The 34-year-old caught Polish opponent Anna Harkowska midway through the 3000m distance.
Having chased down Harkowska, there was no need to complete the race - but Storey had already underlined her dominance by beating her own world record in the morning's heats - the 72nd world record of her illustrious career.
“I didn't expect to be able to catch her as quickly as I did. Hopefully this race will set me up for the rest of the weekend,” said Storey who has three events left at these Games.
"I suppose it did look easy but mentally you have to prepare and make it happen. I have to respect all my competitors.”
Crystal Lane, who competed in the bronze medal race for GB in the same event, was edged out into fourth place by Fiona Southorn of Australia.
Mark Colbourne had earlier claimed GB's first medal of the Games with silver in the C1-2-3 1km Time Trial.
Colbourne, 42, a former Wales volleyball international who injured his back in a paragliding accident three years ago but was competing on the track within a year, came second to Li Zhang Yu of China.
His time would have taken the old C1 world record but Li took five seconds off that mark with a time of one minute 13.009 seconds, reduced by factoring to 1:05.021.
“I’ve worked for the last eight months towards this. A big thanks goes to all the coaches for getting me into the best shape possible,” he said.
“We’ve done this hundreds of times in training and it’s about repeating the process. I probably only heard the crowd on lap three when I had relaxed into my stride.”