Due to the special cavity structure, cyclodextrins become the perfect candidates for biomimic catalyst acting like enzymes. In this paper, hydroxypropyl-beta-cyclodextrin (HP-beta-CD) is used as a phase transfer catalyst for the preparation of glycidyl monostearate (GM) from SN2 substitution reaction by means of the formation of an inclusion complex. FT-IR, (HNMR)-H-1, and GC-MS characterization verified the formation of GM. The calculated inclusion constants of HP-beta-CD/epichlorohydrin and HP-beta-CD/GM inclusion complex were 6.377 and 6709.4 L/mol, respectively. Then, a series of characterizations further demonstrated the formation of a stable inclusion complex. Therefore, the catalytic mechanism of GM synthesis using HP-beta-CD as catalyst was confirmed. The experimental results show the yield of GM can reach 92.6% under the optimum reaction conditions. The kinetics demonstrates the interactions between HP-beta-CD and substrate. The feasibility of HP-beta-CD as a biomimic catalyst will provide a new direction for the synthesis of monoglyceride.