Abstract: HMCM-22/MCM-41 composite molecular sieves with mesoporous and microporous structure were prepared under hydrothermal conditions from HMCM-22. Physicochemical properties of the as-synthesized catalysts were characterized by XRD，N2 adsorption-desorption and NH3-TPD. Results showed the existence of well-structured microphase MCM-22 zeolite and mesophase MCM-41 in the composite materials. Selective alkylation of toluene with dimethyl carbonate (DMC) was carried out over HMCM-22/MCM-41 composite molecular sieves in a fixed-bed flow reactor. Effects of reaction conditions on the alkylation of toluene with DMC were investigated. The selectivity to p-xylene was higher than m- and o-isomers over HMCM-22/MCM-41 which exhibited good catalytic activity and selectivity.