A facile and versatile route to prepare porous polymer microparticles with tunable pore size and density through the combination of phase separation and emulsion-solvent evaporation method is demonstrated. When volatile organic solvent (e.g., chloroform) diffuses through the aqueous phase containing poly(vinyl alcohol) (PVA) and evaporates, n-hexadecane (HD) and polystyrene (PS) in oil-in-water emulsion droplets occur to phase separate due to the incompatibility between PS and HD, ultimately yielding microparticles with porous structures. Interestingly, density of the pores (pore number) on the shell of microparticles can be tailored from one to hundreds by simply varying the HD concentration and/or the rate of solvent evaporation. Moreover, this versatile approach for preparing porous microparticles with tunable pore size and density can be applied to other types of hydrophobic polymers, organic solvents, and alkanes, which will find potential applications in the fields of pharmaceutical, catalyst carrier, separation, and diagnostics.