"I'm so excited to win such a prestigious event and join the likes of Huck Seed, Chris Ferguson and Phil Hellmuth as Heads-Up Champion," said Duke, who became the first-ever woman to win the NBC Heads-Up title.
"I came into this tournament really focused and it feels great to finally break through in this event."
The road to victory at Caesars Palace was not an easy one for the UB sponsored pro. She beat 2008 runner-up Andy Bloch in the first round before getting past 2009 WSOP Main Event runner-up Darvin Moon in the round of 32.
Next up was 2007 champion Paul Wasicka who looked to have the best of Duke when she was all in with ace-ten against his pocket aces at one point. Miraculously, Duke went runner-runner to make a straight, take the lead and eventually move on.
"I would have loved all of my matches to be easy," said Duke. "I'm sure (Producer) Mori (Eskandani) is happy though, because it's going to give the show some serious drama.
"One thing's for sure, I can never complain about bad beats again after hitting that runner-runner king-queen against Paul Wasicka."
In the end, Duke beat eight-time WSOP bracelet winner Erik Seidel in the best-of-three final to bank the $500,000 first-place prize.
"Annie was my number one pick to win," said Seidel. "She played very tough. She had no fear. She really played the way you're supposed to play in this sort of structure."
A mother of four, Duke took some time off from her career as a professional poker player to film The Celebrity Apprentice last season.
Now she says a little time away from the game did her a world of good.
"I know what my main priority is and that's my family, so I'm never going to play as much poker as everyone else, but it's really nice to come back with a bang," she said. "I took the time off, I readjusted and now I've had some good results."
Vanessa Rousso made runner-up at the Heads-Up Championship in 2009, the deepest finish by a woman in the event before this year.
Duke said it's great to see so many female poker players rising to the top.
"I think it's great that a woman came in second last year and a woman finished first this year to really represent woman players," she said. "There are some great female poker players out there."
NBC's coverage of the 64-person event will air Sunday's at 12 p.m. ET beginning April 18 through May 23.
- With files from Matthew Showell