Acrylic latexes with epoxy and carboxyl groups have been synthesized via a two-stage emulsion polymerization process. Different contents of glycidyl methacrylate (GMA) were introduced by three addition modes to copolymerize with methyl methacrylate, butyl acrylate, acrylic acid (AA) in the presence of K2S2O8. To obtain stable latexes, NaHCO3 was employed as a buffer to compensate for the acidity from the thermal dissociation of K2S2O8, and triethylamine was used to neutralize the carboxyl acid from AA. The results showed that the stable latexes with core/shell structure were synthesized by this method, and higher GMA content or addition at earlier stage led to forming the latexes with higher content of coagulum and bigger sized particles. During the formation of films, the polymer epoxy groups underwent the crosslinking reaction with carboxyl acid. When the GMA content increased or GMA was introduced at a later stage, high crosslinking extent was formed in the films. As a result, the crosslinking provided the films with improved water resistance, chemical resistance, tensile strength, hardness, abrasion resistance, and thermal stability.