“Walk This Way” distinguishes itself from other recent fashion-as-art installations, such as the new “The Golden Age of Couture: Paris and London 1947–1957” exhibit at London’s Victoria & Albert Museum or “Fashion Show: Paris Collections 2006,” the MFA’s blockbuster winter exhibit. The idea is not simply to facilitate museumgoers’s gawking at a lovely set of square-toed silk-satin slippers manufactured by the Parisian firm Viault Esté and leave it at that. The MFA already went that route in its 1978 just-the-shoes gallery show, “Stepping Out,” in which it displayed the bulk of its historic footwear collection. Rather, “Walk This Way” requires the consideration of the period footwear in relation to the dress and culture of the times, whether it’s a strappy pair of suede sandals owned by Marilyn Monroe or a Nubian thong dating back to the Byzantine period.

While some juxtapositions require a bit more conjecture — such as the leather-and-linen English women’s tie shoes decorated with a “counted thread” embroidery technique that matches the seat cover of an American side chair from the late 1700s — a good portion of the 28 pairs of shoes included in “Walk This Way” offer a clear connection between the footwear and the art. A couple of wood-inlaid kabkabs (bath stilts) are placed alongside the willowy, bare-backed woman in Jean-Léon Gérôme’s “Moorish Bath” in the MFA’s second-floor European gallery. Within the 19th and 20th century American wing, there are two tiny sets of doll shoes trimmed with ribbon and beads and manufactured in France in the 1870s. They’re placed in a case next to John Singer Sargent’s iconic “The Daughters of Edward Darley Boit,” in which one little girl is absorbed in play with an exquisite china doll. Larissa Ponomarenko’s bedazzled pointe shoes from her performance in the Boston Ballet’s Cinderella this past fall are adjacent to Degas’s petite “Little Dancer” sculpture.

But the installation does dig deeper with some pairings, explaining, in a quirky manner, the underlying reason for a certain shoe’s style. The MFA links two beautifully preserved Venetian chopines (an early version of the high heel) with a postcard-perfect depiction of a Venice canal by Canaletto (“Bacino di San Marco”). The only thing the image lacks, in this context, is a hint of the city’s population — say, hordes of rich women tottering to the shops in their platforms. Still, the relationship explains the significance of the drastic shoe height — in Venice, water is everywhere, and what proper lady would want to find herself with wet toes? Of course, the chopine had a symbolic function, as well. The shoe heel could soar to as high as 20 inches, and thus required any fashionista who dared sport them to hire an attendant on whom she would balance to keep from falling. If only we could get a better sense of this here — the idea is especially funny when considered in light of a Hollywood personal-assistant’s duties. Wintour and moguls like P. Diddy have their own umbrella holders. And, in addition to making Starbucks runs, Britney Spears’s various handlers are expected to ensure she doesn’t land on her ass when she’s dancing tipsily in her cowboy boots on a table at Club Hyde.

“Walk This Way” also creates scenarios where a pair of shoes are matched with another pair of shoes. Take, for example, the Italian women’s “slap-sole” shoes from the 1600s included in the collection. They’re leather, embellished with silk, metallic embroidery, and intended solely for indoor wear. The MFA matches them with a similarly conceived Marc Jacobs platform wedge, crafted in Italy for his 2006 collection. The coupling confirms the influence of the past design on Jacobs’ present inspiration, and the obvious effect the old continues to have on the new. But it also proves a bigger point about bending the rules. Fashion royalty is no longer what it once was. An Italian courtesan of the 17th century would likely have been expected to sport these extravagant slap-sole shoes as a matter of course — such finery, for her, would have been the norm.

Yet the personal taste of the current queens of the best-dressed list can get a bit more unpredictable. Gambling with one’s appearance suggests that you’re in the top echelon of the fashion elite: a conventionally cute piece isn’t always as desirable as an article that can be considered witty, distinctive, crazy, or, just really, really ugly. Kate Moss, the super-waif who has graced hundreds of magazine covers, could easily get away with wearing the Marc Jacobs platforms one day, and the next, be photographed tooling around London in a pair of Crocs — those ill-conceived, plastic clogs that resemble garish blocks of rainbow-colored Swiss cheese, and make even the quintessential design muse appear unfuckable. Nevertheless, Crocs and cocaine have done little to take away Moss’s power. I doubt Catherine de Medici would have gotten away with either.

In 1930, the MFA became the first American museum to separate its textile and fashion department from the decorative arts. Today, the department is at work expanding its assortment of footwear — Whitley says they want to build an encyclopedic collection that’s equally strong in contemporary shoes, like the gorgeous (and ridiculous) Miu Miu wedges made of red-patent leather, brass, and carved wood, and the patterned Vivienne Westwood pumps with six-inch heels in “Walk This Way.” Both pairs are as pretty to look at as they are excruciating to imagine wearing. Here, it’s a relief to see them encased behind glass instead of in a shoebox, even though they remind me of a cat stripped of its claws — overly domestic and dangerous to no one, but beguiling all the same.