Sullivan broke the world record in Monday's men's 4x100m relay but it was reclaimed again by Frenchman Alain Bernard in yesterday's semi final.
But Bernard only held it for a matter of minutes, as Sullivan regained the record, clocking 47.05 in his own semi-final.
Also in contention is veteran Dutchman and two-time defending champion Pieter van den Hoogenband who qualified third fastest.
If van den Hoogenband wins the 100m he will become the first man to win the same event at three Olympic Games.
Australian head coach Alan Thompson says there is a chance the winner could break 47 seconds.
"Who knows what's going to happen in the final," he said.
"A lot more pressure in the final. Who knows, and these guys have got to put it all together."
The women's 100m freestyle world record holder Libby Trickett says the pressure of swimming in an Olympic final could be an issue.
"Obviously being an Olympic final there'll be a lot more pressure and a lot more riding on it, so I'm not sure we'll see faster," she said.
"I hope we do because it's bloody exciting, but it's going to be a great race no matter what happens."
Jessicah Schipper also has a chance to add to her 100m butterfly bronze medal when she races in the 200m butterfly final.
Schipper qualified second fastest behind local favourite Zige Liu, while another Chinese swimmer Liuyang Jiao will pose stiff competition in lane three.
Brenton Rickard is also an outside medal chance in the 200m breaststroke facing 100m champion Kosuke Kitajima.
Finishing off the morning's finals in the pool will be the women's 4x200m freestyle relay with the US and France set to battle it out for gold.
In today's semi-finals, Leisel Jones and Sally Foster race in the 200m breaststroke, Hayden Stoeckel and Ashley Delaney in the 200m backstroke and Trickett and Cate Campbell in the 100m freestyle.
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