Jiao Li, 42, prevailed 4-0 in an all-Dutch final against Jie Li while Melek Hu beat Slovakia’s Eva Odorova 4-1 to win bronze for Turkey.
The Dutch pair also claimed silver in the team event earlier in the Games.
"I told Jie, 'No matter how tired we are, we can't make a fool out of ourselves in the singles'," Jiao Li told reporters at the Baku Sports Hall.
"We're very close friends. But I knew I had to think about the match if I wanted to win. Now that it's over, we can be friends again.”
Li’s gold medal also secured her qualification for the Rio 2016 Olympic Games.
"It means a lot less anxiety and energy spent, knowing that I've qualified."
In the men’s singles, Germany’s Dimitrij Ovtcharov beat Belarusian Vladimir Samsonov 4-3 while Chinese-born Lei Kou won bronze for Ukraine with a 4-2 win against Team GB’s Paul Drinkhall.
Earlier in the European Games, Ovtcharov was in the German side that lost the bronze medal match to Austria in the team event.
After collecting singles gold he criticised the format for the team competition.
"It is ridiculous to play with two players," he said. "We lost through strange regulations that I hope will be changed in the future."
Drinkhall, ranked 22 in Europe, was a surprise finalist and said that despite losing 4-2 and leaving Baku empty handed the sport had a bright future in Britain.
“It's been a great 12 months for us and I think it's only a matter of time before we really take off and do something," Drinkhall, who won the mixed doubles gold medal at the 2014 Glasgow Commonwealth Games alongside wife Joanna, told reporters.
A marathon final game featuring a string of breathtaking rallies finished 22-20, the longest of the tournament, in favour of the Ukrainian.
(Reporting by Tom Hayward; editing by Toby Davis)
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