These are the fifth straight Olympics in which Rhode, 33, has won a shooting medal. She becomes the first American to medal in five straight Games.
With thick clouds rolling over the range and with moisture in the air, Rhode was perfect through the first two rounds of qualifying. She then missed one target during the third round, but her score of 74 out of 75 gave her a commanding lead going into the 25-shot finals.
One after another, Rhode picked off the flying targets in the finals until she had struck them all, giving her a score of 99 -- the best recorded during the four times women have contested this event at the Olympics.
Rhode won the silver medal four years ago in Beijing in a competition that took place in a pouring rain.
Prior to that, she had won three medals in double trap, an event no longer on the Olympic program. She captured gold in Athens, bronze in Sydney and gold in Atlanta 16 years ago.
Wei Ning of China won the skeet silver medal after beginning the finals in fourth place. She missed two targets during the finals and still moved up.
Slovakia's Danka Bartekova won a shootoff with Russia's Marina Belikova for the bronze.
In the other shooting final contested Sunday, Guo Wenjun of China won gold in women's 10-meter air pistol with a score of 488.1. Celine Goberville of France finished second and Olena Kostevych of Ukraine was third.
China won four of the 12 medals awarded in shooting during the first two days of Olympic competition.