Several kinds of N-doped/undoped TiO2 photoelectrodes with different nanostructures have been successfully prepared by anodization method and plasma-based ion implantation (PBII) technique. The morphology and structure of as-prepared photoelectrodes were studied by scanning electron microscopy, X-ray diffraction, and ultra violet/visible light diffuse reflectance spectra. Electronic structure and optical properties were calculated by means of first-principle. Photocatalytic (PC) and photoelectrocatalytic (PEC) performance were measured by the decomposition of terephthalic acid (TA) and Rhodamine B under xenon light illumination. Theoretical calculation results demonstrated that crystal phases have great influence on the electric and optical properties, and N-doped TiO2 photoelectrodes have isolated N-2P impurity states nearby the top of the valence band. The optical properties and UV/Vis analysis confirmed that the absorption edge of N-TiO2 emerged red-shift and high photosensitivity. The discrepancy of PC and PEC performance of as-prepared TiO2 photoelectrodes were ascribed to band gap narrowing, N-2p impurity states, self-semiconductor coupling effect, and long-range ordered orientation of photogenerated carries originated from applied electric field.