Porous titania microspheres (surface area: 36.7 m2/g, average pore volume: 0.30 mL/g, average pore diameter: 32.2 nm, average diameter: 3.5 microns) with a very narrow particle size distribution, were synthesized by refluxing polymerized-induced colloid aggregation (PICA), with octadecyltrimethoxysilane in toluene as a solvent for 8 h, and octadecyltitania stationary phase (ODT) was obtained. The carbon content and hydrophobic selectivity of the stationary phase were 2.87% (i.e. 0.66 mumol/m2) and 0.4638, respectively. ODT showed good chromatographic performances when it was used to separate the neutral and basic solutes using methanol solution as a mobile phase.