In 1992, he received the title of Grandmaster after tying for first place in the 1990 Russian National Championship. Since then, Kharlov has won the 1996 European Club Cup and the 1998 Russian Club Cup with the Kazan chess team. In 2000, he tied for second in the Russian National Championship in Samara and tied for first in the European Individual Chess Championship in Saint-Vincent. He participated in the FIDE World Chess Championship 2000, where he was knocked out by Veselin Topalov in the second round. In the FIDE World Chess Championship 2004 he advanced to the fifth round (final eight), but was again knocked out by Topalov. In 2005 he ended shared first in the Aeroflot Open, only to lose the title on tie-break.