Canada's Camryn Rogers claimed the gold with a best throw of 76.97 metres, while American Annette Nneka Echikunwoke took the silver with 75.48m.
China's Zhao Jie finished third with a best effort of 74.27m, just ahead of Włodarczyk, whose best throw was 74.23m on her fifth attempt.
"I ran out of luck today," the Pole said after the competition. "I gave it my all and battled, but it wasn't enough" she added.
Her fourth-place finish was the best result for Polish track-and-field athletes at the Paris 2024 Olympics so far.
"I think these will be my last Olympics, because I don't suppose I can last four more years," the 38-year-old told reporters.
"But I'm not ending my career yet because I want to compete in the world championships in Tokyo next year," she said.
Anita Włodarczyk. Photo: PAP/Adam Warżawa
"In two days I'll turn 39, but as you can see, one can still compete in the Olympics and beat much younger competitors at this age," she also said.
Włodarczyk returned to action in Paris after missing most of the season due to injury.
The 2012, 2016 and 2020 Olympic gold medalist holds an impressive world record of 82.98m.
At the Tokyo 2020 Games, the Pole won gold with a best throw of 78.48m.
(gs)
Source: TVP, IAR, PAP
