During the ceremony, Simpson shared the stage with cohost (and rumored former love interest Dane Cook) while her ex-husband, Nick Lachey, who was nominated for several awards, sat in the front row.
In fact, both Simpson and Lachey were nominated for choice hotties – and could have had to appear onstage together – but neither won in that category. Instead, Jessica Alba and Orlando Bloom took home those awards.
Before the ceremony, Simpson and Lachey managed to steer clear of each other on the red carpet, as well. Simpson, who made her appearance around 4:15 p.m., trotted around with her mom Tina and hairstylist Ken Paves, who shouted "We love you, Jessica!" behind her on the carpet.
Lachey, with only his publicist in tow, did not appear on the carpet until 45 minutes later – just minutes before the live broadcast began.
For More on the Teen Choice Awards
Once in the audience, Lachey sat front and center, next to Jessica Alba and her boyfriend Cash Warren, where he remained until he was presented with the choice love song award for his single, "What's Left of Me." During his acceptance, a clip from his music video ran, showing girlfriend Vanessa Minillo.
Onstage Lachey joked, "I just want to start about by saying ... awkward? A little bit." (Later Simpson won for choice breakout female star in a movie for The Dukes of Hazzard.)
Perfectly at ease, however, was the final presenter of the evening, the pregnant Britney Spears. Signature gum in mouth, she introduced her husband, Kevin Federline, who closed the night with a performance of his song, "Lose Control."
"This show has been very good to me and my career over the years. And I'm hoping that it will be as good to our next performer," said Spears.
And, with that, Federline appeared, sporting a loose white shirt and white hat and a an ensemble of high-stepping young dancers.
"I ain't here to brag," Federline rapped in a tough-guy style before his number – and the awards show itself – came to an end.
2006 Teen Choice Awards Winners
Action adventure - Pirates of the Caribbean: Dead Man's Chest
Actor, drama/action adventure - Johnny Depp, Pirates of the Caribbean: Dead Man's Chest
Actress, drama/action adventure - Reese Witherspoon, Walk the Line
Actor, comedy - Johnny Depp, Charlie and the Chocolate Factory
Breakout, female - Jessica Simpson, Dukes of Hazzard
Chemistry - Jennifer Aniston and Vince Vaughn, The Break-Up
Liplock - Keanu Reeves and Sandra Bullock, The Lake House
Rumble - Will Turner (Orlando Bloom) v. Commodore Norrington (Jack Davenport), Pirates of the Caribbean: Dead Man's Chest
Summer movie, action/adventure - Pirates of the Caribbean: Dead Man's Chest
Comedy/musical - High School Musical
Reality - American Idol
Actress, drama/action adventure - Rachel Bilson, The O.C.
Actor, comedy - Wilmer Valderrama, That '70s Show
Personality - Ashton Kutcher, Punk'd
Actress - Mischa Barton, The O.C.
Breakout show - So You Think You Can Dance
Breakout star - Zac Efron, High School Musical
Chemistry - Vanessa Anne Hudgens and Zac Efron, High School Musical
Summer TV series - So You Think You Can Dance
Single - Fall Out Boy, "Dance, Dance"
R&B artist - Rihanna
Rock group - Fall Out Boy
R&B/hip-hop track - Nelly Furtado, feat. Timbaland, "Promiscuous"
Rock track - Fall Out Boy, "Dance, Dance"
Love song - Nick Lachey, "What's Left of Me"
Breakout, female - Rihanna
Song of the summer - Nelly Furtado, feat. Timbaland, "Promiscuous"
V Cast Music artist - Nelly Furtado
Hottie female - Jessica Alba
Hottie male - Orlando Bloom
Comedian - Adam Sandler
Red carpet fashion icon, female - Jessica Alba
Red carpet fashion icon, male - Nick Lachey
Choice grill - Brooke Hogan
Action sports athlete, male - Shaun White