Polystyrene cross-linked divinyl benzene (PS-co-DVB) microspheres were used as an organic template in order to synthesize photocatalytic TiO2 microspheres and microbowls. Photocatalytic activity of the microbowl surfaces were demonstrated both in the gas phase via photocatalytic NO(g) oxidation by O-2(g) as well as in the liquid phase via Rhodamine B degradation. Thermal degradation mechanism of the polymer template and its direct influence on the TiO2 crystal structure, surface morphology, composition, specific surface area and the gas/liquid phase photocatalytic activity data were discussed in detail. With increasing calcination temperatures, spherical polymer template first undergoes a glass transition, covering the TiO2 film, followed by the complete decomposition of the organic template to yield TiO2 exposed microbowl structures. TiO2 microbowl systems calcined at 600 degrees C yielded the highest per-site basis photocatalytic activity. Crystallographic and electronic properties of the TiO2 microsphere surfaces as well as their surface area play a crucial role in their ultimate photocatalytic activity. It was demonstrated that the polymer microsphere templated TiO2 photocatalysts presented in the current work offer a promising and a versatile synthetic platform for photocatalytic DeNO(x) applications for air purification technologies. (C) 2014 Elsevier B.V. All rights reserved.