Porous organic microspheres for use in HPLC are formed by coacervating a colloidal silica sol in a uniform mixture of the sol and a polymerizable organic material. The silica particles which formed the sol are removed from the microspheres with ammonium bifluoride. The remaining organic microspheres are rigid, have uniform pore sizes and distribution, and do not swell or shrink in the presence of the solvents used in HPLC.