In 1990, De Biasi became youth team coach for Bassano; in 1991, he was appointed by Vicenza to coach the "allievi nazionali" youth squad. In 1992, De Biasi made his debut as first team coach, being boss of Serie C2 club Vastese (now Pro Vasto); this was followed by three seasons as Carpi boss. In 1996, De Biasi was appointed coach of Serie B club Cosenza, but was fired on Christmas' eve day. After a two-year spell at SPAL, De Biasi was contacted and hired by Serie C1 club Modena on 2000; with the "canarini", De Biasi obtained two consecutive promotions that brought Modena back in Serie A after 38 years. For his achievements with Modena, he was the awarded the "Silver Bench" award in 2002. He left Modena in 2003, after having led his club to safety, achieving an impressive 13th-place finish in the Serie A table, and signed for Brescia, where he had the opportunity to coach Roberto Baggio in his last playing season of his career. He was sacked during the 2004–05 season.