Abstract: We adopted the anion surface active agents SDS, SDBS and mixed surface active agent polyoxyethylene alkyl vinyl double ammonium (PAVDA) to treat polystyrene (PS) monolayer microspheres and improve the distribution of ozonized PS-PVA double emulsion in the oil. The influences of various surface active agents on the contact angle and different absorption rates of PVA on PS film were tested and analyzed. Moreover, the effects of electrostatic repulsion and special resistance on the distribution of monolayer microspheres were also studied. Experimental results show that all of above-mentioned surface active agents can improve the distribution of PS monolayer microspheres to some extent. As for double emulsion treated by SDS and SDBS, because of the flocculation which happened in the oil phase during curing, it was difficult to form large-size microspheres. Specially, we gained about a half surviving rate of PS-PVA double-layer hollow microspheres (700-900 m in diameter), when treating them with PAVDA solution. The results also indicate that space hindrance is more effective than electrostatic repulsion to modify the distribution of PS microspheres.