The efficacy of the supported antimony, bismuth catalysts and unsupported antimony salt for catalyzing the benzylation reaction using benzyl chloride has been studied using microwave irradiation. The benzylation of aromatic compounds with benzyl chloride proceeded to afford diphenylmethane and its derivatives in high yields. The zirconia alone in the absence of antimony and bismuth oxides was little active. Comparing activities of zirconia, Sb/Bi supported zirconia and SbCl3 as catalyst shows that supported zirconia catalysts gave higher conversion than their corresponding unsupported catalysts. XRD and IR results showed that the hydrous zirconia sample exhibited poor crystallinity with a mixture of monoclinic and tetragonal phases. On the other hand, the Sb, Bi promoted samples exhibit prominent lines due to tetragonal phase. Higher activity of supported zirconia catalyst is attributed to presence of greater amount of tetragonal phase of ZrO2, redox potential and higher surface acidity.