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The 26-year-old defeated South Korea's Kim Kyung Ah 6-11, 11-9, 9-11, 11-5, 5-11, 11-7, 11-7 to justify her top seeding in the tournament.
But the Olympic medal hopeful was not allowed to speak to the media, after winning the US$98,000 (S$133,000) tournament early yesterday morning (Singapore time).
The event did not feature the world's top five women players from China.
Singapore Table Tennis Association (STTA) officials in Santiago threw a protective shield around Li, declining an interview request from The Straits Times with the player.
They felt that recent criticism of her mental strength and lack of a killer instinct had been unjustified.
Said STTA's high performance manager Antony Lee: 'Jiawei needs the help of the media in her Olympic dream. She is gunning for a medal, which could be Singapore's first in 48 years.
'It's not fair to say that she needs to finish off her opponents quickly. To us, a win is a win. It does not matter if she beats her opponent in straight sets or over seven sets.'
Singapore's only Olympic medal was weightlifter Tan Howe Liang's bronze in Rome in 1960.
On her acrimonious break-up with Susilo, Lee said the paddler had put the episode at the back of her mind.
Lee said: 'The coaching staff and I have counselled her and we have seen her bouncing back in her performances.
'We will do all that we can to keep Jiawei and the team on track for the Olympics.''
In last week's Brazil Open final, Li was beaten by compatriot and world No6 Wang Yuegu, who did not take part in the Chile Open.
Coupled with her public spat with Susilo, the defeat in Belo Horizonte raised question marks over Li's state of mind for her Beijing mission.
But, in Santiago, she showed steel to claw back from a set down thrice before clinching the seventh set against Kim, the world No16.
The victory ought to give Li a huge boost as the South Korean had denied her a bronze medal in the Athens Olympics four years ago.
Said Lee: 'The Korean favoured a chopping style, which gave her a variety of returns.
'But we instructed Jiawei to work on the opponent's weak backhand, which would limit her range of returns.
'To her credit, Jiawei kept her composure and patiently fought her way to victory. She showed real fighting spirit.'
The victory could improve her world ranking of eight when the tables, as well as her Olympic seeding, are published soon.
Li, Wang and 21-year-old rising star Feng Tianwei, the world No12, have already qualified for Beijing.
Li's upcoming assignments will be in China, Japan and South Korea next month.
She will be back in June for the Singapore Open, before jetting off to Osaka for six weeks of centralised training in the final leg of her Olympic preparation.
Her win yesterday was tempered by her defeat in the women's doubles final.
Partnering Sun Beibei, the duo lost 9-11, 15-13, 5-11, 11-8, 5-11, 5-11 to Hong Kong's Jiang Huajun and Tie Yana.
But there was good news for Singapore's Gao Ning and Yang Zi, who put Hong Kong's Cheung Yuk and Li Ching to the sword in the men's doubles final.
Gao and Yang won 11-6, 11-5, 11-7, 5-11, 11-2.
