After an electrifying "Super Saturday," Bolt and his rivals for the blue riband event of track and field are poised to serve up more pyrotechnics as 80,000 fans pack the Olympic Stadium.
Barring major surprises, the starting line-up for the 9.50pm (0850 GMT) showpiece could feature five men who have clocked a blistering 9.8sec or faster, including world record holder Bolt.
The Jamaican defending champion strolled through his opening heat on Saturday, but faces a menacing threat to his supremacy from compatriot and world champion Yohan Blake.
With former world record holder Asafa Powell and American duo Tyson Gay and Justin Gatlin in the field, the stage is set for a classic sprint duel.
"I am the Olympic champion and I have to show the world I am the best," Bolt, 25, in a bullish eve-of-Games statement of intent.
Sunday's athletics programme kicks off with the women's marathon at 11:00 am, starting and finishing in the Mall in central London, near Buckingham Palace, and taking in many of the city's most famous landmarks.
The powerful Kenyan team features 2011 world champion Edna Kiplagat, last year's world silver medallist Priscah Jeptoo and Mary Keitany, the fastest woman in the world this year.
The Kenyans are also hot favourites to continue their dominance in the men's 3000m steeplechase, a race they have won in every Olympics dating all the way back to Los Angeles in 1984.
A total of 23 medals will be decided on Day 9 of the Games, where other highlights include the men's singles tennis final at Wimbledon between world number one Roger Federer and British hope Andy Murray.
Murray will attempt to add to Britain's burgeoning gold medal haul barely one month after losing to Federer on Centre Court in the final at Wimbledon.
The Scotsman also has the opportunity to win two golds in one day when he partners Laura Robson in the mixed doubles final later Sunday.
"In tennis we're used to thinking the next week we have another chance. But with the Olympics you're not guaranteed another chance," said Murray.
The final two medals in one of the Olympics other racquet sports, badminton, will be decided when China's world number one Lin Dan faces Malaysian rival Lee Chong Wei in the latest instalment of their long rivalry.
In men's and women's artistic gymnastics, the apparatus finals for men's floor and pommel horse take place either side of the women's vault.
Elsewhere, women's boxing will make its debut in Olympic competition with the opening bouts in the women's flyweight and lightweight categories.
Meanwhile, delirious British newspapers hailed the country's greatest ever day at the Olympics, with heptathlete Jessica Ennis featuring as the poster girl on all the front pages.
Red, white and blue were the colours splashed all over the host nation's press as it went into a patriotic frenzy over the six gold medals the British team won on Saturday, including three in athletics.
The Sun tabloid called the gold medallists "The Six Pack", with the headline next to a picture of Ennis showing what it called her "washboard stomach".
"Our finest Olympic hour" was the headline in The Sunday Times, which featured a special souvenir cover wrap consisting of a giant photograph of a beaming Ennis with her arms raised in triumph.
On the front page itself was a picture of Greg Rutherford's unexpected gold medal-winning long jump, while the paper said it was "one of the greatest days in British sporting history".
The broadsheet had a separate box on the front for 10,000-metre gold medallist Mo Farah, describing how his journey "started on the streets of war-torn Somalia" -- he was born in Mogadishu.
Sunday was also the first day of Michael Phelps' new life after the most successful Olympian of all time quit swimming.
"Through the ups and downs, I have achieved everything I ever wanted to do," said Phelps who ended his career with 22 Olympic medals, 18 of them gold.Medals table.
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