What Makes Blake Lively Look Like a 'Potato Sack?'

Blake Lively has made headlines this year for her expanding lifestyle empire, Preserve, and has fashioned herself as kind of a humble foodie (yep, she made pal Beyoncé a “bee” birthday cake and hangs with Martha Stewart), but after chatting with the 27-year-old actress about her spot on our Best Dressed list, it’s clear that the field she’s an expert in is fashion.

“It’s such a passion of mine,” she tells PEOPLE. “That’s the reason I don’t have a stylist, not because I think I can do it better than any of these people, but because I just love it so much that it would be like handing over something.” And leave it to Lively to meld two of her favorite worlds: cuisine and couture. “It would be like making a cake and then handing it off to someone else to ice and decorate,” she explains. “Why would you do that?”

Working sans stylist truly lets Lively chart her own red carpet course. “I look at the whole story — I won’t say ‘journey’ because I saw Anna Wintour’s 73 Questions [Vogue] video (ed note: that’s the word Wintour wishes banned from fashion vocabulary) — when doing any sort of press tour or when doing multiple events, and say ok, how can I diversify these looks?” she says. “[I want] to make them exciting but also not totally manic.”

Tony Barson/FilmMagic

One stop on her multi-gown, ahem, journey at the Cannes Film Festival in May was a graphic yet classic Gucci Première confection (above) she wore to the premiere of husband Ryan Reyonlds‘s film The Captive. “It might be my favorite look I’ve ever worn,” she says. “I just love that old school glamour.”

It was the gown’s “old school” charm that made it one of her contenders for the 2014 Met Gala, where she wore a different stunning Gucci Première designk. “It was Charles James-inspired. If you look at the martini silhouette, you can identify that,” she explains of the black fluted accent down the center of the gown. “But because of the theme, there was a risk that someone might be wearing something similar.” True story: even Blake Lively has to consider ways to avoid a fashion faceoff.

In case you often find yourself wondering, “Is there anything that Blake Lively can’t wear?” (like the editors at PEOPLE do on a daily basis), she says that yes, there is a style the star strays away from.

“There are things that I see on Kate Moss and think, ‘I have to have that,’ but when I try it on me I look like a potato,” she reveals. “I don’t like to wear things that don’t look right on my body … that 1920s drop waist, or even ’60s mod. If you don’t cinch in the waist it looks like I’m just hiding, you know, animals? I just start to look like the cargo part of an airplane.”

The closest you’ll get to seeing Blake go mod/as a cargohold was her Michael Kors look at the CFDAs, which she says was her “faking the ’60s” because she gave the shift silhouette a little bit of a waist.

RELATED PHOTOS: See the rest of the Best Dressed list!

Mike Coppola/Getty; Dominique Charriau/WireImage

Another standout look of Lively’s was not seen on the red carpet, but on the streets of New York City (right photo above). It’s a Valentino coat emblazoned with butterflies and “Fastissima” booties by her go-to shoe designer, Christian Louboutin, that Lively explains “change colors as you move.”

“Those shoes were at Christian’s atelier in Paris, and [when] I went into the store they were in a glass box spinning with a light on them,” she shares. “I felt like Dorothy seeing the ruby slippers, and he took them out and put them on me.”

She was permitted to wear them to a Chanel event that evening, and then, yes, she was allowed to keep them. “It was so generous. I’m still dying. I go into my closet and look at those shoes all the time,” she says. But the gift wasn’t a true Cinderella-glass-slipper moment. “I’m just going to say it right here, they’re a size too small! I lied and was like, ‘They fit perfectly!’ It’s very rare that I get to keep the stuff I wear, so those shoes are a huge huge deal.” As for the Valentino coat? It went back: “Oh my gosh, I didn’t get to keep that one,” she says with a sigh.

After the Dorothy reference about her Louboutins, and seeing the Balmain mini (center) she wore for her self-described “coming out” as a brand ambassador for L’Oreal Paris, you might have guessed Lively’s got a thing for the yellow brick road. “I’m far too obsessed with the Wizard of Oz,” she says. “So having baby blue and white gingham and adding hand embroidered crystals all over that? I mean, come on. It’s like the modern day Parisian Dorothy.” And though “Balmain can be very strong and dominating and sexy,” she says, “there was sweetness to this one.”

For more from Lively on her amazing looks from this year and the rest of the best dressed list, pick up PEOPLE’s Style Issue, on stands now. And tell us: What’s your favorite Lively fashion moment for the past year?

–Catherine Kast