Thompson, who sprinted to gold in the 100m on Saturday, stunned Dutch world champion Dafne Schippers to win the 200m in 21.78sec.
Schippers, who stumbled dramatically as she crossed the line, took silver in 21.88 while Tori Bowie of the United States won bronze.
The victory was the latest golden night for Jamaica, who 24 hours earlier had been celebrating Omar McLeod's 110m hurdles victory.
Thompson, 24, dedicated her victory to the trailblazing Jamaican stars who had won Olympic gold over the past years.
It was a first Olympic women's sprint double since American world record holder Florence Griffith Joyner's at the Seoul Games in 1988.
Thompson's gold also avenged her loss to Schippers in the World Championships in Beijing last year.
"I knew she had a strong finish, so I knew I had to get out there as soon as possible," Thompson said of her Dutch rival.
- Bolt in the groove -
======================
Jamaica's golden games is likely to continue on Thursday with Usain Bolt looking unstoppable in his signature event, the 200m.
Bolt eased up 40 metres from the line to finish ahead of Canada's Andre De Grasse -- and believes his world record of 19.19sec could be in jeopardy in Thursday's final.
"I definitely think I can try for the world record, I definitely feel that," he said.
But there was a shock as Bolt's US rival Justin Gatlin -- the fastest man over the distance this year -- failed to make the final.
In the final event of the night, 2013 world champion Rollins led a majestic performance by America's formidable trio of 100m hurdlers.
The American women hugged each other and jumped up and down after the sweep was confirmed.
"It's like a sisterhood," said Rollins. "I've known these girls for years. I'm so grateful and blessed that we were able to accomplish this together."
It was the first clean sweep of the event in Olympic history.
- Reese upset -
===============
Elsewhere Wednesday, Tianna Bartoletta of the United States upset defending champion and team-mate Brittney Reese to take the long jump gold.
"It's just a great feeling to have pulled that off," said Bartoletta. "It's been a good night for sure."
But it was a disappointing long jump final for Darya Klishina.
The only Russian athlete allowed to compete in the track and field competition following her country's doping scandal bowed out midway through the final.
In the day's other final, Conseslus Kipruto of Kenya won gold in the men's 3,000m steeplechase.
Evan Jager of the United States won silver, while Mahiedine Mekhissi of France was awarded bronze after Kenya's Ezekiel Kemboi, who had crossed the line in third place, was disqualified.
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