The 29-year-old, who placed an agonising fourth at the past two Games, pursued home favourite Leon Marchand to finish second in their heat.
The final starts at 19:30 BST on Sunday evening, before Britain's Adam Peaty goes for a third consecutive Olympic gold in the 100m breaststroke at 20:44.
The first appearance of 22-year-old Marchand at these Olympics created a raucous atmosphere at La Defense Arena.
The crowd chanted the French sensation's name and waved their tricolore flags as the poster boy of the Games, who is chasing four golds in the next eight days, won comfortably, with Litchfield 1.21 seconds adrift.
Marchand broke the world record in this event last year, in doing so taking the last remaining record held by American great Michael Phelps.
He is now coached in the US by Phelps' former mentor Bob Bowman, having sent a letter to the 59-year-old American prior to the last Olympics asking for help.
Litchfield missed the Commonwealth Games and World Championships in 2022 because of a still undisclosed "personal issue", but broke the British record at the Olympic trials in April.
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