Chili raced in the 500cc class for several years on a Gallina HB Honda with partial works support. His most notable 500cc result came at the 1989 Grand Prix of Nations, which he won after most of the leading riders withdrew over concerns about a dangerously slippery track surface. His best championship finish in the premier class was sixth in 1989. He subsequently dropped to the 250cc class, where he finished third overall in the 1992 championship.
Chili switched to the Superbike World Championship in 1995, riding a private Ducati. In his debut season he won at Monza — the first of what would become a remarkable personal record at that circuit — took three more podiums, set the fastest lap in four races, and finished eighth in the championship.
Over the following years he built a consistent if occasionally frustrating record. In each of the 1995, 1996 and 1997 seasons he won the second race at Monza having crashed in the first — a coincidence that became something of a personal signature. In 1996 he recorded two wins and his first two pole positions, finishing sixth. In 1997 he won three races and took three poles but finished seventh.
His best season came in 1998, when Chili rode for the factory Ducati team. He won five races and finished fourth in the championship, his career-high result. The year was undermined at Assen, where intense racing with Carl Fogarty — also on a factory-backed Ducati under a separate team — ended in a fall on the final lap, and Chili was released by the factory at the end of the year. He joined Suzuki for 1999, winning twice including at the A1-Ring, and finished sixth.
In 2000, Chili returned to near his career-best form, recording ten podiums and again finishing fourth overall, this time without a win as Colin Edwards dominated the season. The following two years were less productive, yielding just three podium finishes across the two seasons and seventh- and eighth-place final standings. In 2003, approaching 40 years of age, he showed renewed competitiveness with five third-place finishes and one win, finishing seventh. The 2004 season with the PSG-1 Ducati team produced five overall with nine more podiums. He joined the Klaffi Honda team in 2005, finishing tenth, before a broken pelvis in 2006 forced him to miss several rounds and effectively ended his competitive career.
After retiring at the end of the 2006 season, Chili became team manager of the Guandalini Racing team in World Superbikes for 2009. His career total of 17 wins, 10 poles, and record start count establish him as one of the most durable and competitive figures in World Superbike history, despite never winning the championship.