A novel fumed silica-supported bidentate arsine rhodium complex was prepared by treatment of poly-4-oxa-6,7-dichloroheptylsiloxane with potassium diphenylarsenide in THF and then reaction with rhodium chloride. It was found that the title complex is an efficient catalyst for hydrosilylation reaction of olefins with triethoxysilane and can be reused several times without noticeable loss of activity. (c) 2006 Elsevier B.V. All rights reserved.