The 39-year-old - who split from boyfriend John Mayer last month - is playing a Fatal Attraction style stalker on the hit comedy.
At one point the actress made quite a scene on set, tackling one of her male co-stars with gusto.
Crazed: Jennifer Aniston filming a guest spot on 30 Rock in New York yesterday
She's already won over the show's star and executive producer, Tina Fey, who said: 'Jennifer is not only incredibly lovely to have around, she also has what the young people would call 'mad skills.'
Aniston, who rose to fame as Rachel on Friends, will play Fey's room mate Claire Harper in the episode.
Free-spirited Harper shows up in New York and rapidly attaches herself to Alec Baldwin's character Jack Donaghy.
Scream queen: The actress plays a Fatal Attraction style stalker
The announcement that Aniston would be returning to NBC was made last week, by NBC Entertainment's executive vice president Teri Weinberg.
'She is the perfect comedic talent to work with the Emmy-winning 30 Rock cast.
'This promises to be a memorable, hilarious night of comedy.'
Aniston's last primetime TV acting role was on best friend Courteney Cox's series Dirt.
The real-life friends shared a kiss when Aniston guest-starred on the show last year.
30 Rock, which has won Emmy, Golden Globe and Screen Actors Guild Awards, returns to US TV screens on October 30.
Making friends: Jennifer has already won over her costar Tina Fey, who describes her as 'incredibly lovely'
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