Many more viewed giant screens erected near the palace and down at Monaco's port, as the couple exchanged a kiss in the presence of Albert's two sisters Princesses Caroline and Stéphanie, who shed a tear.
Minutes later, they appeared at the palace balcony for another kiss while Prince Albert blew a second one to the cheering crowd.
Philippe Narmino, president of Monaco's Council of State, who officiated, spoke of his "joy" about the union in both English and French – a language the new Princess can barely speak a word of.
Before the 5pm ceremony, Mr Narmino said: "It's the event of my life. As a magistrate who has dealt with hundreds of divorce dossiers during 27 years, I will be marrying a couple for the first time."
Monaco is hoping the "fairytale" wedding will lift the recently gloomy economic situation in the world's second smallest state after the Vatican, which is only one tenth the size of Disneyland Paris.
"Monaco is glamour, luxury, exception. It's in our DNA. This will help us project a more rounded image," said Michel Bouquier, Monaco's tourism chief.
But according to French press reports, the couple almost failed to tie the knot over claims Albert may have fathered a third illegitimate child.
A senior detective from Monaco told Le Figaro newspaper that "Charlene had her passport confiscated so that the Prince's entourage could persuade her to stay" after they stopped her at Nice airport last week with a one-way ticket to South Africa.
Albert's first two love children and their mothers stayed away from Friday's ceremony and are expected to be absent from the star-studded Catholic ceremony on Saturday to spare them "media exposure".
Guests are expected to include French President Nicolas Sarkozy, James Bond star Roger Moore, former supermodel Naomi Campbell, and fashion designers Karl Lagerfeld and Giorgio Armani, who designed the wedding dress for the Saturday's religious ceremony.
The £45 million celebrations surrounding the wedding included a concert by The Eagles on Thursday night and another by Jean-Michel Jarre on Friday night.
Multi-Michelin-starred superchef Alain Ducasse will provide a seafood and vegetable meal for 500 lucky guests at a gala at Monaco's opera house.
The French press has compared the event to Britain's Royal Wedding – lamenting the fact that the Duke and Duchess of Cambridge was forced to decline their invitation to Monte Carlo because they were on an official trip to Canada.
Princess Charlene met Albert at a swimming competition in Monaco in 2000. Both share a love of sport, with Prince Albert competing in Monaco's Olympic bobsleigh team. "I was 22 and focused on my sport. I wasn't in the emotional place for a relationship," Charlene said last year."But the moment I met Albert I felt a profound sense of destiny. I have been quoted as saying I felt weak at the knees. This is a slightly trite way of phrasing it, but it is true I knew he was 'The One'."
Aside from France's President Nicolas Sarkozy and the kings and queens of Sweden and Belgium, the crowd included fashion designers, models, sportsmen, more minor royals and senior officials from the tiny principality.
Organisers hoped the glamour of the spectacle would distract from gossip after Monaco officials privately admitted there is "truth" in a rumour that Albert faces a paternity test following a claim by a pregnant former lover.
Reports the princess was furious and threatened to leave when she learned her prince's latest secret had overshadowed the build-up to the wedding, but the event itself has gone smoothly and the Monegasques are philosophical.
Organisers admitted, however, that there had been a "hiccup" in preparations following an incident at Monaco's heliport, but did not confirm reports that Charlene had contemplated fleeing home to South Africa.
"We can't remake the prince. It's a modern marriage. Charlene has known him for a long time and accepts it," shrugged a 30-something wellwisher, insisting on remaining anonymous like many of Monaco's 7,810-strong native population.
Albert, at 53, is two decades older than his blonde bride and has two children from previous relationships.
But even if a third or a fourth is confirmed he will still not have an official heir until his lawful wife bears him one.
"We just want the Grimaldi dynasty to continue," said a 72-year-old Monegasque, a direct descendant of a group of Genoan migrants who settled the rocky Riviera outcrop and future tax haven in 1775.
Guests arrived in a cavalcade of 200 BMW 7 Series limousines and striding across the red carpet towards the palace, with early arrivals including Czech supermodel Karolina Kurkova and retired tennis ace Henri Leconte.
Pop star Jean-Michel Jarre received warm applause from locals still grateful for the previous night's spectacular concert. Heels were high, hats were broad and many guests seemed to have ignored a request for covered shoulders.
The bride had appeared tense but poised at her civil marriage ceremony on Friday in the throne room of her palace, but relaxed slightly at a buffet for Monaco's people, where she posed for pictures and hugged babies.
Later, she and the prince joined an estimated 80,000 people, double the normal population of the state, at the waterfront for Jarre's show.
The wedding feast will be held at the opera house opposite the casino
.
For the Sunday brunch that will cap the wedding festivities in Monaco, known as a magnet for the rich and famous, the princess is expected to wear a Giorgio Armani Prive silk satin duchesse in bright green, with pleat detail on the bodice and skirt.
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