As biodiesel production from triglyceride transesterification increases, by-product glycerol is accumulated, motivating the development of novel mechanism for converting glycerol into valuable chemicals. In the present work, for the selective production of acrolein from glycerol, SiO2-coated HZSM-5 molecular sieve with preciously controlled surface was designed. As characterized by NH3-TPD and pyridine adsorption IR, the total acid and the Lewis acid amounts of SiO2-coated HZSM-5 were decreased whereas the Brønsted acid amount remained almost unchanged. SiO2-coated HZSM-5 catalyst exhibited selectivity to acrolein of 64%, in glycerol conversion of 100% under reaction temperature of 300°C, much higher than HZSM-5 catalyst with acrolein selectivity of 52%. The catalytic activity durability was also improved by the modification of the surface properties because SiO2 coating reduced the surface acid amount and the micropore volume of HZSM-5, suppressing side reactions and inhibiting carbon deposition efficaciously.