ABSTRACTCore‐double shell structure poly(vinyl acetate‐butyl acrylate) emulsion was prepared by semicontinuous emulsion polymerization, and the effects of ethyleneglycol dimethacrylate crosslinker (EGDMA) on the emulsion particle structure and film performance were studied systematically. The emulsion particles' structure was characterized by transmission electron microscopy and Fourier transform infrared spectroscopy, and the particle size and distribution were characterized by Zeta potential—particle analyzer, as well as analysis of the film mechanical properties, water resistance, thermal properties, and so on. The results show that, when 0.1 and 0.5% EGDMA were added to the inner‐shell and outer‐shell reaction stage under the core‐double shell P(VAc‐BA) emulsion preparation process, respectively, it led to a more clear core‐double shell structure and a larger particle size (about 500–800 nm) of emulsion particles, and the comprehensive performance of the P(VAc‐BA) emulsion showed better. This work provided some insight into modifying the surface properties of the emulsion particles, which may expand the application field of the emulsion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41899.