In the years since, she's been a red-carpet rebel, jeans-wearing mum, bikini globetrotter and Versace model. Now her style evolution has come full circle, and Moore is the star of the Ann Taylor fall ad campaign.
She is the latest Hollywood connection for a company that previously tapped Katie Holmes and Naomi Watts to court its shoppers. "I feel like I've known Ann Taylor since I was a kid. I've watched the clothes move into support for the working woman," said Moore, 48, during a break at a recent photo shoot in LA.
"It used to be a lot of suiting. I've seen as we've changed, that they've changed, reflecting on how we live as modern women, which is wearing things that take us from day to night, from workout to work to weekend."
Looking at Moore's own fashion history, she's changed a lot, too. She has done the menswear thing, the retro siren and many plunging necklines. She's been bald and buff — and totally bare. (Remember the Vanity Fair cover when she was pregnant in 1991?)
In recent years, she has developed more of a signature look — one that's both sophisticated and sultry — which has won her praise from fashion insiders.
"We have to remember it's okay to take risks. Sometimes it will work and sometimes it won't. For me, I know there's a certain kind of balance of criteria. I like things that are classic. I want to know that I'll look in my closet five years from now and that piece still has a place. I don't have room or time for something's that just absolutely of the moment."
Cues from the past
She has no problem taking some cues from the past, though. "I look at Katharine Hepburn, from the '30s and '40s, and the women of the '70s, Bianca Jagger," said Moore. "When we're young, we're finding ourselves, what we like. I can say there are certain things that remain a constant. I've always loved vintage. I've rested in a place that's classic, with a twist."
That's the look you see in the Ann Taylor ads, shot by top photographer Patrick Demarchelier at one of Rockefeller Centre's rooftop gardens in New York City against a backdrop of towering buildings.
In one ad, the star of movies Ghost and A Few Good Men stands confidently, hands on her hips, wearing a '60s-esque beige wool cape and a black blouse edged in lace.
In another shot, she sports a sexy-chic long V-necked grey sweater accented by faux fur. Moore hadn't worked with Demarchelier since he photographed her as the cover of an issue of Harper's Bazaar in the '90s, one of her favourite shoots, she said.
The collection also includes animal-print jackets, tailored tweed, wide-legged pants and bling-y statement jewellery. Married to actor Ashton Kutcher, with three daughters from her ex-husband Bruce Willis, Moore said she definitely identified with Ann Taylor's working-mum demographic.
Looking like a casual mum herself during her break on the LA photo shoot, she charmingly wore Harry Potter-ish designer black round glasses and loose-fitting jeans. On set, she transformed, moving fluidly into poses, doing yoga stretches between takes.
There's back-and-forth style advice between her and her daughters, including oldest Rumer Willis, a budding actress featured in ads for Badgley Mischka's spring 2011 collection.
"There are things that I might wear with flats that they would put with heels," said Moore.
"They definitely stay at a kind of cutting edge because they're still in that experimental stage, which is important to remember. You keep going outside your comfort zone. When you get too confined to ‘This is what I know works and looks good,' I think you also don't stay fresh and current."
Moore still can push the envelope. For example, to this spring's Costume Institute Gala at the Metropolitan Museum of Art, she wore a strapless Prabal Gurung gown dripping in black feathers topped by a Philip Treacy head piece.
"Some of the kind of unspoken rules of what we're allowed to do at this age, and what you can get away with, really comes down to what's in your comfort zone, what makes you feel good about you," Moore said.