Riding on a watertaxi dubbed "Amore", the celebrity pair crossed Venice's Grand Canal at around 3pm on Friday, gliding up to the Hotel Cipriani on the island of Giudecca, where they will be hosting A-list guests for a gala dinner.
The silver-haired actor, director and producer, was seen helping his father Nick Clooney onto a "vaporetto" boat, as they headed into the first night of the nuptials, set to draw out over the weekend.
Travelling with them was the ex-supermodel Cindy Crawford, one of dozens of stars to have flocked to Venice -- paparazzi in tow -- for the wedding of the world's most sought-after catch and his human rights lawyer fiancee.
Brad Pitt, Angelina Jolie, Sandra Bullock and Matt Damon, will also be checking in to the Cipriani before the gala meal rustled up by Italian chef Riccardo de Pra.
Damon was among the first guests spotted at Venice airport on Friday, along with Clooney's cousin Miguel Ferrer and the "Spin City" stars Ellen Barkin and Richard Kind.
The 53-year-old actor and Alamuddin, 36, are expected to be officially married in a civil ceremony on Monday, but the city of masks is preparing for a weekend of serious partying before then.
Sources said the actor would be celebrating with 136 guests at a reception on Saturday at the fresco-adorned Aman hotel, an exclusive seven-star hotel in the 450-year-old Palazzo Papadopoli.
"Clooney's on everyone's lips here in Venice, the girls in particular are all in a tizzy, they'll be lining the banks of the canal to see him," said watertaxi driver Bruno Bartolini.
Guests will be escorted by police boats to the exclusive seven-star Aman on Saturday, to keep over-excited Clooney admirers and hundreds of photographers at a distance.
They'll be met with lashings of fizz and canapes in the garden, an oasis sheltered from the bustle of the canal, before sitting down in the main library to a sumptuous five-course dinner, according to a source close to the hotel.
George Clooney and his Lebanon-born British fiancee Amal Alamuddin take a taxi boat upon their arrival in Venice. (Getty)
The Aman's restaurant will be turned into a nightclub, where they'll dance the night away, a source said, with Lana Del Rey reportedly preparing to serenade the couple.
Speed boats will be banned from stopping in front of the hotel to keep goggling to a minimum.
Rome's former mayor Walter Veltroni, a long-term friend of Clooney's, will be performing the civil ceremony, which is likely to be held in the town hall, the stunning Ca' Farsetti 14th century palace opposite the Aman hotel.
The streets around the town hall will be off limits to the public from 12 noon for two hours on Monday, when the ceremony is expected to take place.
US actor George Clooney and his Lebanon-born British fiancee Amal Alamuddin (Getty)
Though the world's most famous waterway will not be closed entirely, there were grumbles in the northern Italian city over the disruption and such an ostentatious display of wealth in times of economic crisis.
"Clooney's not bringing us bread for our tables," said 16-year-old Viviana, "coming here with all his nice money while we can't find jobs."
Alamuddin, who moved to Britain with her family as a three-year-old, met the Hollywood star through his humanitarian work.
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