The campaign, which was created by Rainey Kelly Campbell Roalfe/Y&R, also stars Marks & Spencer regulars Laura Bailey, Erin O'Connor and Noemie Lenoir.
The spot shows the five models wearing items from the new collection, including lingerie and accessories, in a number of luxurious settings, including the train's richly panelled corridors and an opulent dining car.
The Orient Express was chosen to appear in the ad to reflect the retailer's new range, in which the emphasis is on sensual, sumptuous fabrics from satin and velvet to rich wools and silks.
The TV spot closes on a shot of the women in a boat on one of Venice's canals, with the song, "Look-a-There, Ain't She Pretty" by The Charioteers, providing the soundtrack.
Steve Sharp, executive director of marketing at Marks & Spencer, said: "The backdrop of both the Orient Express and the beautiful city of Venice has added a whole new dimension to the campaign, which oozes chic, timeless style and luxury and is a perfect way to showcase our amazing autumn and winter collections."
Richard Exon, the incoming chief executive at RKCR/Y&R, said: "I've long admired the M&S advertising and it has been great seeing our M&S team, headed by Mark Roalfe, create another visually stunning campaign that builds on the momentum of the previous work, whilst imbuing it with its own distinct seasonal style."