The eight-girl team, judged on execution and overall impression, racked up an overall points total of 98.833 in Rome's scorching heat.
Spain, looking resplendent in their multi-coloured costumes, snatched silver after entering the pool with the pressure on as the penultimate team.
The bronze went to China while the Canadian team danced for joy on the poolside after finishing a surprise fourth.
The swimming events at the 13th World Championships begin next Sunday.
On Saturday, Paola Espinosa beat Chinese favourites Chen Ruolin and Kang Li to win the women's 10-metre platform event and become Mexico's first ever diving World champion.
The mighty Chinese team bounced straight back though when Olympic champions Qin Kai and Wang Feng retained their men's three-metre synchronised springboard title later in the day.
Espinosa took command with her third dive and made sure of victory with an excellent fifth and final dive, giving her a score of 428.25 points after Olympic champion Chen threatened to pinch it with a superb final effort.
Chen finished on 417.60 while her compatriot Kang took bronze with 410.35.
"I am very happy because I competed several times against the Chinese girls and this time I managed to beat them," Espinosa, who won bronze in the 10-metre synchronised with Tatiana Ortiz at the Beijing Olympics, told reporters.
Wang and Qin dominated the men's synchronised 3-metre from start to finish and ran out easy winners with a score of 467.94.
Troy Dumais and Kristian Ipsen of the United States won silver while the Canadian pairing of Alexandre Despatie and Reuben Ross completed the podium.
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