The model, 48, flaunted her pins in a sleek off-shoulder cocktail dress as a water taxi dropped her and her husband Tom Kaulitz, 31, off at the star-studded event.
Leading the way, Heidi showed off her physique in the glittering gown, which featured a leg split, sparkling fringe and a semi-sheer silvery-hued skirt.
She teamed the look with a chunky black medallion and various elaborate rings, also showing off her expertly manicured pink nails.
She added extra height to her already lofty frame with chunky black heels.
Heidi wore her blonde locks in sleek lines around her features, which were made up with a creamy foundation, a nude lip and a thick lashing of mascara.
Tom went for a crisp white open-collar shirt tucked into black slacks, carrying a matching blazer over his shoulders.
Leading the way: Heidi showed off her physique in the glittering gown, which featured a leg split, sparkling fringe and a semi-sheer silvery-hued skirt
Coupled up: Tom went for a crisp white open-collar shirt tucked into black slacks, carrying a matching blazer over his shoulders
Preened: She teamed the look with a chunky black medallion and various elaborate rings, also showing off her expertly manicured pink nails
Chic: Tom finished things off with shades and statement black and gold loafers
Tom finished things off with shades and statement black and gold loafers.
The duo were careful to navigate their entrance as they stepped off the boat and onto the jetty, which they used as a catwalk to enter the event, which is taking place in St Marks Square in the city, with the beautiful architecture as a backdrop for the runway.
Dolce & Gabbana are hosting a weekend-long event, with Heidi and Tom at their Saturday night party the night before.
She wore a diamond-adorned evening gown, sharing snaps of the event to Instagram, captioning this, ‘THANK YOU [Dolce and Gabbana] for the most beautiful night,’ and added an Italian flag and red heart emoji.
The highly anticipated two-day fashion event will feature fashion shows showcasing the brand’s latest collections: Alta Moda, Alta Sartoria, Alta Gioielleria, and Alta Orologeria.
Saturday night: Dolce & Gabbana are hosting a weekend-long event, with Heidi and Tom at their Saturday night party the night before
Shhhh! Heidi and Tom secretly married in 2019 who she called after two marriages, her ‘match.
Sweeping in: She stepped onto her water taxi in her dramatic ensemble
Assistance: She was accompanied by a pair of sharp-looking guards
Meanwhile, Lady Kitty Spencer looked radiant as she arrived at the show.
The niece of Princess Diana, 30, donned a gorgeous cream knee length dress which boasted sequin florals and dripped in beading.
Lady Kitty’s appearance comes after her honeymoon stay at a £3,590-a-night hotel in Italy following her wedding to millionaire businessman Michael Lewis, 62.
Lady Kitty carried her belongings in an embellished box bag and accessorised with stunning dangly diamond earrings.
Stunning: Lady Kitty Spencer, 30, looked radiant as she arrived at the show in Venice
The British aristocrat, who is a spokesmodel for the Italian fashion house, elevated her statuesque figure with silver heeled sandals which had a buckle at the ankle.
The English rose flashed a subtle smile for the camera as she headed into the fashion show.
Elsewhere, Kourtney Kardashian, 42, put on a street-side fashion show as she hit the bridges of Venice with her rocker boyfriend Travis Barker, 45, en route to the event.
The reality star certainly caught the attention of onlookers in a black miniskirt, which featured red floral prints. Highlighting her ample assets in a jet black leather top, the five-foot-one socialite elevated her height with a coordinating pair of silver spiked heels.
Perfect match: Kourtney Kardashian flashed her toned legs in a black floral miniskirt as she caught the Venetian sights with her dressed-down beau Travis Barker on Sunday
Hot stuff: Kourtney had styled her beautiful brunette locks into bob with a middle-parting and protected her eyes from the beaming sunlight with a set of oversized sunglasses
Classic: Kourtney had thrown a bulky chained clutch over her right shoulder for the very stylish outing
The Poosh founder brought Calabasas to the ‘City of Water’ as she firmly gripped Travis’s hand, who cut a casual figure in a charcoal motif-printed T-shirt.
The Blink-182 band member paired the number with a pair of black pinstripe trousers, featuring a white illustrated patch.
Kourtney was later spotted boarding a luxurious boat, where Travis patiently waited. She was given a helping hand by a crew member as she elegantly made her way onto the vessel. The model waved at onlookers as she headed to her next destination while Travis cheekily cradled her derriere.
Elegant: The television personality was given a helping hand onto a luxurious boat by a crew member