N-Vinyl-2-pyrrolidone (NVP) and maleic anhydride (MA) copolymers were synthesized via radical polymerization. The synthesized copolymers were grafted with methoxypolyethylene glycol (MPEG) chains of different average molecular weights (350, 550, 750 Da). The grafted copolymers were used as surfactants in the synthesis of poly(ε-caprolactone) (PCL) nanoparticles in water by solvent evaporation technique. In order to further test the synthesized surfactants, the miniemulsion polymerization of vinyl acetate was performed. Two methods of obtaining miniemulsion were employed: a sonicator and a static mixer. The synthesized surfactants performed well in both type of experiments while in the case of static mixer nanoparticles with a lower polydispersity were obtained. Droplets with a mean diameter of 250 nm were obtained when using the sonicator while the static mixer led to formation of droplets with a mean diameter of 600 nm.