The Iraq war veteran, who also appeared as Brot Monroe on daytime drama All My Children, triumphed over reality TV star Rob Kardashian and his professional partner Cheryl Burke, who finished in second place. Talkshow host Ricki Lake and her professional partner Derek Hough ranked in third place.
> Digital Spy live blogs part 2 of 'Dancing with the Stars' season 13 final
Martinez said: "Oh, man. First and foremost, I want to thank everyone who voted for us for ten weeks. Thank you America, for believing in us."
Turning to his professional dance partner Karina Smirnoff, he added: "You are so amazing... I'm so pleased to have been a part of your first mirrorball trophy."
Kardashian said: "I'm so thankful... [this was] a crazy experience. I'm definitely not sad, I've won in my book."
Burke added: "I love him so much, we're going to stay friends for ever."
Kardashian had topped the judges' leaderboard after Monday night's show with 57 out of a possible 60 points. He also ranked top of the leaderboard on Tuesday's show after all four dances had been completed, with 113 out of a possible 120 points to Martinez's score of 112.
> Digital Spy live blogs part 1 of 'Dancing with the Stars' season 13 final
Lake, who finished in third place, said that she had "loved basically every minute" of the competition, while Hough said that his celebrity partner was "an absolute winner", adding "she's knocked it out of the ballpark the entire season".
On Tuesday night, each of the contestants performed their favourite dance of the season, before Kardashian and Martinez - who had the highest combined total of judges' scores and viewer votes - performed an instant samba.
Grammy award-winning country trio Lady Antebellum performed their hit single 'Need You Now' on the show, and also aired new track 'Dancing Away with My Heart' for the first time on American television.
Eliminated contestants Hope Solo, David Arquette, Nancy Grace, Chaz Bono, Carson Kressley, Kristin Cavallari, Elisabetta Canalis, Chynna Phillips and Ron Artest also returned to perform once again.
In a close Digital Spy poll, 38% of readers who voted thought Kardashian would win the show, with Martinez second on 31.5% and Lake polling third with 30.5%.
The season 14 premiere of Dancing with the Stars will air on March 19, 2012 on ABC.
> 'Dancing with the Stars' finalists talk chances on Kimmel: Video