The polymer/nano-inorganics composite microsphere possesses excellent application prospects, but it is difficult to resolve the problem of the aggregation of nano-inorganic particles in polymer and the affinity between inorganics and polymer matrix. In this study, the preparation and characterization of polystyrene (PS)/ethylene vinyl acetate copolymer (EVA)/CaCO3 microspheres fabricated via a novel phase inversion emulsion process are described. By this one-pot method, the PS/EVA/CaCO3 microspheres are obtained by firstly converting styrene monomer containing EVA and nano CaCO3 into droplets dispersed in water with help of emulsifiers and a following polymerization. Because the inorganic nanoparticles are ultrasonically dispersed in liquid monomer mixture before the polymerization, the aggregation of nano-inorganic particles could be prevented to a great extent. The EVA is designed to enhance toughness of polystyrene matrix and increase the affinity between polymer and inorganic particles. The morphological structure of PS/EVA/CaCO3 microspheres is that nano CaCO3 particles are embedded both in the interior and on the surface of the microspheres. The micro-sized PS/EVA/CaCO3 microspheres showed a significantly improved mechanical property and a better heat resistance. This technique also offers the possibility for fabricating many kinds of new and useful polymer/inorganic microspheres with tailored performance by using special monomers and inorganic particles.