Electronic structures with the type-II band alignment usually exist only in heterostructures. Using the generalized Bloch theorem, we reveal that an effective type-II band alignment can be induced in the single crystalline TiO2 nanowires (NWs) by an axial twisting deformation. With this, we further reveal distinct responses of the the valence band (VB) states and the conduction band (CB) states in the radial dimension of the nanowire. Specifically, in the twisted NW, the VB states migrate from the NW core toward the NW shell while the CB states migrate from the NW shell toward the NW core. Our results pave a new way to realize the type-II band alignment in single crystalline NWs, which is critical for actual applications such as NW-based photovoltaic effect and photocatalytic effect. Further, the significant variation of the quantum states also illustrates the possibility to tune the electronic properties of TiO2 NWs by strain engineering.