Storey, competing in her ninth Paralympics at the age of 46, won the 18th gold medal of a career that began in swimming by taking the C5 time trial ahead of French hope Heidi Gaugain.
She completed the course in 20min 22.15sec, beating her opponent by more than four seconds.
She also extended her record as the most successful British Paralympian, ahead of swimmer Mike Kenny's 16.
Born without a functioning left hand, Storey has now won 29 Paralympic medals of all colours since she made her debut at the 1992 Barcelona Games.
Her latest win was her 13th Paralympic gold in cycling, with the other five from swimming.
"I'm very happy. I am over the moon. But I know that there's always ways to improve things," Storey said.
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