Heterostructured TiO2 materials are of great importance in electronic and photochemical related applications. We report herein a simple, low-cost, and scalable fabrication of metal oxides heterostructured TiO2 nanotube arrays (NTAs) through a combined strategy of thermal decomposition and crystallization. Various MxOy/TiO2 heterostructured films (M = Zn, Ce, Cu, Cr...) were obtained by using TiO2 NTAs as "nano-containers" as well as "nano reactors", while using M(CH3COO) solutions as the precursors. SEM, XRD, EDS results demonstrated that Cu2O/TiO2 NTAs, ZnO/TiO2 NTAs, Cr2O3/TiO2 NTAs, and CeO2/TiO2 NTAs were successfully fabricated. Photo catalytic results revealed that the heterostructured MxOy/TiO2 films could either enhance the UV photocatalytic activities or enable the visible light photocatalytic activities of the TiO2 NTAs. This study provides a facile general approach to prepare MxOy/TiO2 NTAs films, which could be very useful for environmental and energy areas.