A novel photocatalyst, TiO₂ nanotubes with the confinement of the electron donor and acceptor at the inner and outer surface, respectively, was fabricated by a universal method. The as-designed nanostructure afforded a void space separation state of electron donors and acceptors, which remarkably enhanced the photoinduced charge separation, resulting in the enhancement of the catalytic activity for the photooxidation of olefins with O₂.