In this paper, monodisperse poly(styrene-co-acrylmide) (PSAM)/Nb2O5 hybrid hollow spheres were synthesized using a hollowing mechanism similar to the Kirkendall effect. When these hybrid hollow spheres were calcinated at different temperatures, totally different structures, pseudohexagonal TT phase hollow Nb2O5 spheres, and orthorhombic T phase short rods were obtained. Both of them exhibited stronger photocatalytic activity than the commercial Nb2O5, especially the as-obtained Nb2O5 hollow spheres displayed significantly enhanced photocatalytic property and auto-accelerated photocatalytic kinetics compared to the commercial TiO2 (P25). Moreover, the Nb2O5 hollow sphere-based nanofilm fabricated using oil-water interfacial self-assembly presented excellent UV photodetective performance. (C) 2013 Elsevier Inc. All rights reserved.