A semi-interpenetrating polymer network (semi-IPN) combining vinyl acetate–ethylene (VAE) and butyl acrylate (BA), as well as vinyl acetate (VAc), was prepared through emulsion polymerization with the help of self-made dispersant and diethylene glycol diacrylate (DEGDA), the cross-linking agent. Both the dispersant and DEGDA had significant contribution on the preparation of semi-IPN(BA–VAc–VAE). And, the DEGDA had a strong influence on the conversion of polymerization system. The effects of emulsifiers and their amounts on the stability of obtained emulsions have been determined, and the best choices have been made after series experiments. The optical microscopy (OM), FTIR and DSC methods were adopted to characterize the structure and composition, morphology, and Tg of the prepared emulsions, respectively. Various comparisons have been made between the semi-IPN and VAE emulsions, and the experimental results indicated that the semi-IPN(BA–VAc–VAE) had been developed with improved properties in both water resistance and adhesion.