Nitrogen-doped titanium oxide inverse opal structure was synthesized to combine both chemical and physical modifications on n-TiO2 by the polystyrene sphere self-assembly followed by a sol-gel process. Enhanced visible-light absorption and subsequently enhanced photodegradation efficiency were observed in this unique structure, which can be attributed to both nitrogen-doping effect and inverse opal structure effect. Our work suggests that the coupling of photonic band gap structure with photocatalytic materials is a promising approach to achieve maximum enhancement for various photocatalytic materials, especially for environmental applications and solar cell devices.