N-Vinyl-2-pyrrolidone (NVP) and itaconic anhydride (IA) copolymers were synthesized via radical polymerization. The synthesized copolymers were grafted with 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 implied: 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 160 nm were obtained when using the sonicator while in the case of static mixer the mean diameter was 280 nm.