Chili grew up in Bologna and developed into a versatile Grand Prix racer in the Italian domestic scene before graduating to the world stage. His early career highlight came in 1985 when he won the 125 cc European Championship, a title that marked him as a rising talent. He then spent several seasons in the 500 cc World Championship aboard a Gallina HB Honda, receiving some works backing but remaining upper-midfield at best. His standout result in the premier class was victory at the 1989 Nations Grand Prix, a race run in treacherous wet conditions that saw most leading runners withdraw — Chili's best championship position that year was sixth overall.
After his 500 cc years, Chili stepped down to the 250 cc class, where he finished third overall in 1992. That strong showing helped convince the paddock that he retained the pace to compete at a high level, and in 1995 he made the switch to the Superbike World Championship on a private Ducati.
His debut Superbike season was immediately productive. He claimed a win at Monza along with three further podiums and set the fastest lap in four races, finishing eighth overall. A curious pattern emerged during his first three Superbike years: in 1995, 1996, and 1997, he won race two at Monza in each successive season after crashing in the opening race at the same circuit. Despite this recurring first-race misfortune, the results accumulated. In 1996 he collected two wins and his first two poles, rising to sixth in the championship. In 1997 he took three wins and three poles, finishing seventh.
The 1998 season brought Chili a coveted factory Ducati berth, and he responded with five race victories and fourth place overall — the best championship finish of his career. That year, however, also produced one of the more controversial moments of his Superbike tenure. At Assen, a fierce late-race battle with Carl Fogarty, also on a factory-supported Ducati but from a different team, ended with Chili falling on the final lap. The incident strained relations and he was released by the team at year's end.
In 1999 Chili moved to Suzuki, finishing sixth with two more wins, including a characteristic bounce-back: he crashed while leading race one at the A1-Ring, then came back to win race two. The 2000 season saw him match his 1998 tally of ten podiums and again finish fourth overall, though with only a single race win as Colin Edwards dominated the championship.
Between 2001 and 2002, Chili collected only three podiums across the two seasons, falling to seventh and then eighth in the standings. The 2003 campaign offered something of a revival: nearing his fortieth year, he took five third-place finishes and one win, finishing seventh in a competitive field. In 2004, riding for the PSG-1 Ducati team, he achieved his second-best championship result — fifth overall — supported by nine podiums that demonstrated his durability at the highest level.
Chili joined the Klaffi Honda team for 2005 alongside rookie Max Neukirchner, finishing tenth. His final season in 2006 was disrupted by a broken pelvis that forced him to miss several rounds, and he retired at the close of the campaign.
Following his retirement, Chili returned to the World Superbike paddock in a management role, serving as team manager of Guandalini Racing for the 2009 season. In September 2020, he publicly confirmed that he had been diagnosed with Parkinson's disease, news that drew widespread support and tributes from across the motorcycling community.
Chili's Superbike record — 17 wins, 10 poles, and the most race starts in the championship's history at the time — places him among the most recognisable Ducati campaigners of the late 1990s and early 2000s. His tenacious style, willingness to push the limit on the final lap, and ability to remain competitive deep into his thirties made him a fan favourite throughout a Superbike career that spanned more than a decade.