Emulsion and emulsifier-free emulsion polymerization of styrene, N-vinylformamide, and ethylene glycol dimethacrylate are investigated with the goal to form positively charged monodisperse submicron crosslinked particles. The effects of the monomer ratio, the type and concentration of the buffer salt, and the emulsifier concentration on the monomer conversion and on the shapes, size distributions, and surface characteristics of the formed particles are studied. It is shown that, in the surface layers, amino groups prevail over carboxylic groups. The total surface concentration of acidic and basic groups increases with the degree of crosslinking of particles and as a result of their subsequent surface hydrolysis.