Hugh Hefner's ex-girlfriend Holly Madison seemed to be making the most of her newfound freedom as she attended Sunday night's 5th Annual Hollywood Style Awards ... but she didn't look so happy to be hanging out with her potential replacement.

Madison showed up to the event alongside one of the busty blonde twins now rumored to be romantically involved with the Playboy founder (although an insider told us that Madison "can't stand" her).

The girls kept to themselves for most of the event and Madison seemed particularly miserable, although she's obviously cashing in on her "Girls Next Door" fame for as long as possible with a string of hosting gigs lined up over the coming weeks.

Wedding Bells for Justin and Jessica?

The rumor mill has been murmuring that Jessica Biel and Justin Timberlake are getting ready to tie the knot. But an insider told Pop Tarts that while they aren’t engaged, there is “no question” they intend to spend their lives together and are "very much in love."

The happy duo was spotted in Sin City on Saturday night, first dining at Nobu before hitting up the Kings of Leon concert at The Joint in the Hard Rock Hotel & Casino.

“They were kissing and cuddling throughout the whole time,” an eyewitness told Pop Tarts. “Justin would occasionally pump his first into the air and get really into the songs. They just seemed so happy.”

Jessica Simpson a No-Show at Style Awards

More news from the Hollywood Style Awards: Last week, Hollywood Life Magazine announced that Jessica Simpson would be honored as the first-ever recipient of their Hollywood Style Original award. Simpson was to be awarded for both for her personal style and her line of shoes, accessories, fragrance and apparel.

However, the pop star-turned-country crooner was absent from the star-studded ceremony on Sunday night and mysteriously, so was her award. We're told that Simpson had a last-minute scheduling conflict and was unable to make it, and thus had to relinquish her title.

Rachel Bilson was also named last week as a Hollywood Style Icon, but was suddenly "replaced" by Sophia Bush when she too had another commitment. Apparently, the recipient had to be present in order to win the award, so we can't help but question who truly "won" and who so happened to just be available...

The reception and after-party were nonetheless lavish and stylish kick-offs to L.A. Fashion Week with the likes of Sophia Bush, Emmy Rossum, Kristen Bell, Jamie-Lynn Sigler, Eve, Rose McGowan, Molly Sims and Carson Kressley all in attendance to present and accept trophies for their contribution to Tinseltown trendiness.

"90210" newbie Annalynne McCord represented her fellow castmates as they received the accolade for the Hollywood Style People's Choice Award ("reportedly" beating out the Kardashians and the cast of "The Hills"), but the rising starlet was brought back down to earth by the founder of iconic fashion brand BeBe, Manny Mashouf.

After McCord gave a gushing speech in adoration of Mashouf and presented him with the award for Fashion Visionary, he took to the mic and thanked "Mary-Lynne McCord" for her kind words. Guess that proves how much the fashion elite really care for the rehashed television show...

Katy Perry Overcame an Alcohol Problem but Hasn't Gotten Over 'The Hills'

She's sitting pretty at No. 1 on the music charts with her hit single "I Kissed a Girl," but songstress Katy Perry experienced some serious substance abuse issues while waiting for that big break.

"It was really difficult, drinking became a problem," Perry told the upcoming issue of Blender magazine, which hits stands Tuesday. "It got out of control until I said, OK — back to work. I know I'm speaking for someone, even if it is someone silly."

Despite Perry's parents both being pastors, she has chosen not to follow a particularly religious lifestyle, but the 23-year-old Santa Barbara native was also quick to reject any association with "The Hills" stars who also stem from the beaches of Southern California.

"There's no comparison. No offense, but those ladies are a totally different breed," she said. "A cheeseburger's fine if you're just looking for something quick to fill you up, but there's no substitute for the filet!"

Girls Never Liked Pete Wentz in High School

Ashlee Simpson's husband and the father of her unborn baby Pete Wentz is a rock 'n' roll guitarist for Fall Out Boy. But that doesn't mean he did well with the ladies back in the day.

"I liked girls a lot, I just don't know how much they liked me, but I always had a crush," he told Tarts last week while promoting his band's cameo performance in the upcoming "Sex Drive" comedy.

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