We investigated the synthesis of functional, monodispersed polystyrene (PS) spheres by surfactant-free emulsion polymerization. Standard emulsion polymerizations rely on the use of small molecule surfactants to create particles of uniform size. In this study, an amphiphilic block copolymer (BCP), polystyrene-b-poly[(ethylene oxide)-co-(allyl glycidyl ether)][PS-b-P(EO-co-AGE)], was synthesized through anionic polymerization and used as a functional surfactant in the emulsion polymerization to impart functionality to the surface of the PS spheres. The diameter of the PS spheres varied depending on the concentration of BCP used in the reaction. Our studies show that an increase in the concentration of block copolymer concentration resulted in a decrease in the size of the spheres: at 0% BCP the average diameter was 258.7 nm and at 20% BCP the average diameter was 42.5 nm. Adding control over surface functionality with the nanoscopic (40-120 nm) self-assembly and high surface area of PS spheres provides an advanced platform for applications such as new materials for photonics, filtration media, anti-fouling, and energy storage.