The mesoporous molecular sieve Zr-MCM-41 was synthesized under hydrothermal conditions. Zr-MCM-41 material was impregnated using sulfuric acid to prepare SO42-/Zr-MCM-41. The obtained materials were characterized by XRD, FT-1R, N-2 adsorption/desorption and NH3-TPD analysis technique. The results indicated that SO42-/ Zr-MCM-41 was of better mesoporous structure, long range ordering and crystallites, and that SO42- existed in the skeleton of Zr-MCM-41 and enhanced its acidity. SO42-/ MCM-41 were firstly used as catalyst in the esterification of terpineol. The catalytic results were compared with those obtained by using sulfuric acid (33%), HY, HZSM-5 and SO42-/ZrO2 as catalysts. It was showed that SO42-/Zr-MCM-41 were not only of better catalytic activity and selectivity, but also of better regenerable performance. The effects of synthesis methods of catalysts and Si/Zr mole ratio on catalytic properties were also studied. In addition, AlCl3 was supported on the synthesized mesoporous molecular sieves to get composite catalysts that were firstly used to catalyze the polymerization of alpha-pinene. It was showed that the catalytic result of the composite catalyst was better than that AlCl3 alone.