Polyacrylamide-poly(methyl methacrylate) copolymer emulsion was synthesized by prepolymerization of methyl methacrylate, and then copolymerization with acrylamide. The final yield of polyacrylamide-poly(methyl methacrylate) emulsion can be up to 93.69%, and its molecular weight was 11.2 × 104 Da, as well as the characteristic peaks of the ester group (–COO) of methyl methacrylate and amide group (–NH2) of acrylamide appeared on its structure. The component content of acrylamide and methyl methacrylate from polyacrylamide-poly(methyl methacrylate) can be effectively controlled by adjusting the prepolymerization conversion of methyl methacrylate. The polyacrylamide-poly(methyl methacrylate) emulsion exhibited spherical morphology, and its particle size was 50–130 nm. Moreover, the correlation between particle size and the film-forming property of the polyacrylamide-poly(methyl methacrylate) emulsion was studied. It was concluded that when the particle size was small, the aggregation ability among molecules was strong, and endowed polyacrylamide-poly(methyl methacrylate) emulsion film with more action during the stretching process, making it able to withstand the larger tensile opposite force. Interestingly, the polyacrylamide-poly(methyl methacrylate) emulsion can reinforce the adhesion of polyester/cotton yarn. These benefit from the strong hydrogen bond between polyacrylamide and cotton yarn and poly(methyl methacrylate) had a similar ester structure to polyester fibers. This work solves the problems of difficult copolymerization between acrylamide and acrylate, it provides a new way to develop acrylamide-based copolymer adhesive.