A series of rare earth modified tungstosilicic acid catalysts MxH4–3xSiW12O40 (M = La, Ce, Pr, Nd, Sm; x = 1/3, 2/3, 1, 4/3) were prepared by ion exchange method. The structure, stability and acidity of the catalysts (CexH4–3xSiW12O40 ) were characterized by different analytical and spectroscopic techniques such as FT-IR, XRD, TGA-DTG and 31P MAS-NMR, and their catalytic properties were investigated on the esterification of lauric acid (LA) and glycerol (GL) to glycerol monolaurate (GML). Results showed that Ce1/3H3.0SiW12O40 catalyst had the best catalytic activity in the synthesis of GML. The rare earth metal cation (Ce) had been effectively combined to tungstosilicic acid, and the catalysts maintained the complete Keggin structure. Compared with tungstosilicic acid, the acidity of CexH4–3xSiW12O40 catalysts decreased, but the catalysts had good catalytic performance during the esterification for strong Brønsted acidity and Brønsted-Lewis acid synergy. The Ce1/3H3.0SiW12O40 was utilized to optimize the reaction conditions with 78.4% GML yield under GL/LA molar ratio of 4.0, catalyst amount (relative to LA mass) 4%, reaction temperature 423 K and reaction time 120 min. Kinetic studies revealed that the Ce1/3H3.0SiW12O40 for synthesis of GML with an apparent activation energy of 42.37 kJ/mol. The GML yield decreased to 71.4% after five consecutive, the catalyst still had superior reusability in the reaction system.