"I can't believe it! I'm so grateful for the win. I didn't give up," Masai said.
Melkamu won the silver and her compatriot Wude Ayalew was third. Defar had to be satisfied with fifth.
"I'm very disappointed that we lost the gold," said Melkamu. "I would have been happy if Meseret had got the gold. I was expecting her to win. I never saw the Kenyan."
Olympic and two-time defending world champion Tirunesh Dibaba of Ethiopia did not compete because of injury.
The men's shot put gold was won by Christian Cantwell of the United States, who avenged his Beijing defeat by beating Olympic champion Thomasz Mazewski of Poland.
Ralf Bartels earned the first medal for host nation Germany with the bronze.
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