Nice to meet you! Jennifer Garner appears starstruck as she joins former Vice President Joe Biden at charity gala in NYC

Jennifer Garner attended a charity gala in New York on Wednesday night in a strapless black dress.

And despite being one of Hollywood's top actresses, she seemed a little starstruck when she found herself sharing the spotlight with former Vice President Joe Biden.

The 45-year-old beamed as she joined the 74-year-old politician and his wife Dr. Jill Biden at the 5th Annual Save The Children Illumination gala at The American Museum of Natural History.

VIPs: Jennifer Garner seemed a little starstruck when she found herself sharing the spotlight with former Vice President Joe Biden at a charity gala in NYC

VIPs: Jennifer Garner seemed a little starstruck when she found herself sharing the spotlight with former Vice President Joe Biden at a charity gala in NYC

Garner looked stunning in her choice of gown that featured a shimmery bodice and then black tassels that fell to her ankles over the shimmery black skirt. 

The ex-wife of Ben Affleck wore her long brown hair loose with a center parting and sleekly styled and added black sandal heels.

Biden was dapper in a dark two-piece suit with shirt and gray tie while his wife was lovely in a dark green satin dress.

VIPs: Jennifer Garner seemed a little starstruck when she found herself sharing the spotlight with former Vice President Joe Biden and his wife Dr. Jill Biden at a charity gala in NYC

Things to say: She chatted away to Biden as she spent time with him and his wife, Dr. Jill Biden who looked lovely in a dark green gown 

Good cause: Garner posed for photos with the Bidens and Bulgari CEO Jean-Christophe Babin at the Save The Children Illumination gala at The American Museum of Natural History

Good cause: Garner posed for photos with the Bidens and Bulgari CEO Jean-Christophe Babin at the Save The Children Illumination gala at The American Museum of Natural History

Natural beauty: The ex-wife of Ben Affleck wore her long brown hair loose with a center parting and sleekly styled and was made up with smoky eye shadow and dark pink lip color

Natural beauty: The ex-wife of Ben Affleck wore her long brown hair loose with a center parting and sleekly styled and was made up with smoky eye shadow and dark pink lip color

Red carpet ready: Garner looked stunning in her choice of gown that featured a shimmery bodice and then black tassels that fell to her ankles over the shimmery black skirt

Red carpet ready: Garner looked stunning in her choice of gown that featured a shimmery bodice and then black tassels that fell to her ankles over the shimmery black skirt

Earlier, Garner was seen leaving her hotel wearing a black cape over her dress.

She wore a glam make-up look with a nude pout, while keeping her silky brown locks poker straight.

The mother-of-three kept her accessories to a minimum with only a silver bracelet and a ring.

Edgy: Jennifer Garner did just that when she stepped out for an event in New York City's SoHo on Wednesday

Edgy: Garner was spotted earlier in the evening leaving her hotel in the Big Apple wearing a vlack cape over her dress

Leggy: Jen wore a intricate dress that featured a cape top with a fringe bottom

Leggy: Jen stepped out in black sandal heels that revealed her matching black pedicure

Despite Jennifer's cheery front, the actress has recently been caught in the middle of sexual harassment claims regarding her ex-husband Ben Affleck.

A source told E! News on last week that the 45-year-old actress 'is very annoyed because it just means more attention on her and the kids as a result of Ben's actions'.

'She tries to shield them from any and all publicity and scrutiny. She's taking her kids to school and to all of their activities. As far as they know nothing has changed and all is well. That is always her goal but she's been pretty frustrated with him.'

Burton, a former TRL host and One Tree Hill star, shared the allegations, just hours after Affleck made a statement condemning Harvey Weinstein's alleged abusive actions in his sexual assault and harassment scandal.

She wore a glam make-up look with a nude pout, while keeping her silky brown locks poker straight
She wore a glam make-up look with a nude pout, while keeping her silky brown locks poker straight

Upbeat: She seemed in great spirits as she headed to the charity event

The mother-of-three kept her accessories to a minimum with only a silver bracelet and a ring

 Chic: The mother-of-three kept her accessories to a minimum with only a silver bracelet and a ring

In it Affleck said he was 'saddened and angry' over the 'sickening' claims.

Affleck's statement was quickly slammed by a number of people - including Weinstein accuser Rose McGowan who called Affleck a liar.

Although the actress is annoyed at her ex-beau, she continues to put on a united front for her kids.

Last week the former husband and wife were seen taking their kids to get ice cream together. 

Casual cool: Jennifer was later seen leaving the bash in trainers instead of her towering heels

Casual cool: Jennifer was later seen leaving the bash in trainers instead of her towering heels

Comfortable: Jennifer, known for her casual sense of style, appeared comfortable in her sporty flyknit shoes as she returned to her hotel
Comfortable: Jennifer, known for her casual sense of style, appeared comfortable in her sporty flyknit shoes as she returned to her hotel

Comfortable: Jennifer, known for her casual sense of style, appeared comfortable in her sporty flyknit shoes as she returned to her hotel 

Feeling good: She had clearly enjoyed her night at the event, as she returned home with a beaming smile

Feeling good: She had clearly enjoyed her night at the event, as she returned home with a beaming smile

The 13 Going On 30 star and Ben split in 2015 after 10 years of marriage. They officially filed for divorce this year.

Jennifer and the Batman actor co-parent Violet, 11, Seraphina, eight, and Samuel, five. 

Earlier in the day, Jennifer was seen grabbing a cup of coffee in New York City's SoHo.

Jen slipped into a pair of jeans and a black rocker-chic graphic pull-over sweater.

The mother-of-three teamed her ensemble with black leather loafers, as she was seen smiling and chatting with onlookers.

Earlier in the day, Jennifer was seen grabbing a cup of coffee in New York City's SoHo
Earlier in the day, Jennifer was seen grabbing a cup of coffee in New York City's SoHo

Rock on: Earlier in the day, Jennifer was seen grabbing a cup of coffee in New York City's SoHo

Effortless: Jen slipped into a pair of jeans and a black rocker-chic graphic pull-over sweater

Effortless: Jen slipped into a pair of jeans and a black rocker-chic graphic pull-over sweater