In emulsifier-free, emulsion polymerization with ionizable comonomer, the ionization of the comonomer is critical in determining the size of the final polymerie particles at sub-micrometer scale. In this study, polystyrene latex beads with carboxylates on the surface were synthesized using acrylic acid as a comonomer. Specifically, ammonium hydroxide was added to the emulsifier-free polymerization system to promote the ionization of acrylic acid by increasing pH. Smaller polystyrene latex particles were produced by increasing the ammonium hydroxide concentration in the reaction system, due to the enhanced stability promoted by the ionization of acrylic acid during the nucleation step. In addition, the surface morphology of the polystyrene latex particles was controlled by the concentration of acrylic acid, the dissociation of which was influenced by the ammonium hydroxide concentration.