Storey edged French teenager Heidi Gaugain on the line after 71km of racing in the eastern Parisian suburb of Clichy-sous-Bois as Colombia's Paula Ossa Veloza claimed bronze.
The 46-year-old, who was born without a functioning left hand, has now won 30 Paralympics medals since she made her debut at the 1992 Barcelona Games in the sport of swimming aged 14.
"It's amazing, really amazing it's not sunk in at all. I'm delighted my wheel was at the front at the finish," Storey told reporters.
"It was just a matter of holding her as she continued her acceleration, it was a long way out.
"I'm still nippy for a 46-year-old but I use it wisely," she added.
Storey refused to rule out competing at her 10th Games in Los Angeles in 2028.
"I need to enjoy this one first, never say never to anything," she said.
"This needs to sink in because it was one of the most exciting races we've had."
