This study aimed to describe the preparation and characterization of porous titanium oxide particles of narrow particle size distribution by a single-step swelling process of polystyrene template microspheres. In this research, different specific surface areas, porous structures and densities of porous titanium oxide particles had been synthesized with various experimental parameters. Two main parameters were tested and discussed: (1) acetylacetone amount (from 0 to 1 ml) and (2) reaction time (from 2 to 32 h). Polystyrene template particles were polymerized by emulsifier free-emulsion polymerization (a kind of polymerization method). For the swelling process to be successful, a chelating agent (acetylacetone) was added to delay the aqueous hydrolysis of titanium (IV) isopropoxide in the water phase. The influences of various reaction parameters on size, morphology, composition, specific surface area, porous structure and density of particles were investigated. The properties of particles were analyzed by scanning electron microscope, Brunauer–Emmett–Teller, Fourier transform infrared analysis, thermogravimetric analysis, powder X-ray diffraction, and specific gravity meter.