Four nano heteropolymolybdovanadoarsenics were synthesized by solidstate reaction at room temperature.Their general molecular formulas are H3MAsMo10V2O40·xH2O(M=Co2+,Ni2+,Cu2+,Zn2+).The catalytic behaviour of the nano heteropoly compound for hydroxylation of benzene to phenol with H2O2 and the reaction parameters were studied in detail.The experimental results showed that the yield of phenol was over 50% and the selectivity for phenol was over 98% under the optimum conditions with the H2O2/C6H6 molar ratios of 2.0,C6H6/catalyst(mass ratios)of 23,reaction time of 2.5h,and temperature of 70℃.The four nano catalysts had high activity for the hydroxylation of benzene to phenol.