The 53-year-old was accompanied by his father Nick as he made the 15-minute journey from the Cipriani hotel to the seven-star Amal resort, where he was meeting his bride-to-be.
Clooney has officially tied the knot with his British fiancée Amal Alamuddin on Monday afternoon.
He was joined by around 90 guests for the reception, during which the pair exchanged vows followed by a lavish dinner.
The couple were each joined by members of their families as well as friends including U2 singer Bono and fellow actor Matt Damon.
Guests began arriving by chauffeur-driven taxi boats shortly before 6.30pm with Matt Damon the first to arrive.
Cindy Crawford and Rande Gerber wave from a boat as they go to George Clooney's wedding with Amal Alamuddin, in Venice, Italy. Photo / AP
Wave after wave of guests were ferried to the waterfront entrance of the exclusive hotel over a period of 20 mins, which culminated in Mr Clooney's arrival just before 7pm as the sun was setting.
George and his British fiancee, 36, won't officially tie the knot until the civil ceremony said to be hosted at the palatial 14th century Ca' Farsetti palazzo on Monday. The building houses Venice's town hall.
The couple have already requested that guests do not bring mobile phones in a bid to prevent unauthorised pictures being leaked from the event.
Emily Blunt looked red carpet ready in her stunning blue keyhole gown featuring floral embellishment all over the garment. The British actress slicked her hair back into a chic updo and wore gold jewellery and accessories.
Watch: Raw: Guests join Clooney and fiance in Venice
Emily was joined by her husband John Krasinski, also in a tuxedo and the couple joined Matt Damon and his stunning wife Luciana Barroso on the water taxi to the event.
US Vogue editor Anna Wintour opted for a pink, grey, white and black colour theme, matching her fur stole to the pale shades of her dress and accessorising with sparkling jewels around her neck.
Actor Bill Murray was spotted in high spirits as he made his way to the venue on the boat. Chuckling and waving at passers-by, Bill looked like he couldn't wait to get to the event hosted by his The Monuments Men co-star
Actor Bill Murray cruises Canal Grande as he goes to George Clooney's wedding with Amal Alamuddin, in Venice, Italy. Photo / AP
Bono stuck to his trademark black for his evening attire, but chose blue-tinted aviator sunglasses to wear for the night.
Hundreds of locals turned out to line the streets, alleyways and Kerry's along the canal as they cheered on the Ocean's Eleven star, who briefly waved to the gathered crowds.
Bono Vox and his wife Alison Hewson arrive in Venice, Italy. Photo / AP
Mr Clooney's 36-year-old fiancée had remained inside the resort for the duration of the day following her hen party the previous night.
While Ms Alamuddin was busy preparing the event, George had spent the day larking around the nearby Cipriani Hotel with his best man Randy Herber and his wife Cindy Crawford, following his stag night on Friday.
Sporting a wide grin, George, 53, was in high spirits during an al fresco breakfast outside the Belmond Hotel Cipriani on Saturday morning ahead of his imminent marriage to human rights lawyer Amal.
Clooney rubs his hands in the moments before his marriage. Photo / AP
The greying actor was joined by supermodel Cindy Crawford, 48, and her husband, 52-year-old businessman Rande Gerber after a boozy stag do the night before.
George was seen laughing and smiling with his companions before he began to speak with a photographer nearby. When being congratulated on his upcoming wedding, George joked: 'I'm not getting married'.
Curiously, the actor appeared to clutch a gift wrapped object as he departed with his two friends some time later.
The Hollywood star looked fresh-faced despite his late night out the night before which saw him spend his final night as a single man downing tequila shots and vintage red wine with his groomsmen.
During the meal the group were presented with thousands of pounds worth of vintage 2010 Sassicaia red wine, which costs up to £250 a bottle - a wedding present from restaurant owner Giovanni Fracassi.
His best man, Rande, had also brought several bottles of tequila, which the group enjoyed after their dinner at the exclusive eatery.
Meanwhile, preparations are well underway for the big day, with scaffolding being erected around the main jetty of the Aman Canal Grande Venice, which is hosting the wedding party.
Workers could be seen hauling in vast bouquets of ivory flowers, hinting at the colour scheme the pair have opted for.
George's actor buddy Matt Damon was also spotted enjoying a cocktail reception along with the groom at the Belmond Hotel Cipriani on Saturday afternoon.
Actor Matt Damon leaves the Cipriani hotel to go to the George Clooney wedding with Amal Alamuddin, in Venice, Italy. Photo / AP
A fierce bidding war has broken out among the world's biggest celebrity publications, who are all desperate to capture the moment that Oscar-winner Clooney finally says 'I do'.
It is understood that the US edition of fashion bible Vogue has all but secured the rights after bidding well in excess of £1million.
Back in 1989, George married actress Talia Balsam in a wedding officiated by an Elvis Presley impersonator in Las Vegas.
No doubt this time around, the nuptials will be a far more stylish affair, as it is understood US Vogue secured the rights after bidding well in excess of £1 million.
However, there are said to have been further negotiations for a British celebrity magazine to share the rights with a seven-figure offer being made.
- Daily Mail