The direct synthesis of polymer microspheres modified by aramid nanofibers (ANFs) is an interesting challenge. This work describes a simple aqueous process to prepare polystyrene (PS)/ANF composite microspheres, where the specific ANF network was "dressed" on PS. ANF was derived from the copolymerization of terephthaloyl chloride, p-phenylene diamine, and methoxypolyethylene glycol and could be dispersed in water stably. We applied the as-synthesized ANF as a Pickering emulsifier in the o/w emulsion of styrene monomer. Radical polymerization was subsequently initiated in the Pickering emulsion system. The combination of ANF with polymer spheres was revealed by scanning electron microscopy (SEM) and thermal gravity analysis. The role of ANF in the monomer emulsion as well as in the polymerization was studied through SEM, optical microscopy, optical stability analyzer, and pulse nuclear magnetic resonance combined with the polymerization kinetic analysis. Moreover, we investigated the effects of other synthesis parameters, such as monomer type, monomer content, pH value, and salt concentration.