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A photoelectrochemical device was achieved by interfacial self-assembly of macrocyclic π-conjugated copper phthalocyanine (CuPc) on surface of TiO 2 nanorod arrays (NRs). The photocurrent density of the elegant TiO 2 @CuPc NRs photoanode reaches 2.40 mA/cm 2 at 1.23 V vs. RHE under the illumination of 100 mW/cm 2 from AM 1.5G sun simulator, which is 2.4 times higher than that of the pure TiO 2 . At the same time, the photoelectrochemical device constructed through this strategy has good stability and the photocurrent density remain almost no decline after 8 h of continuous operation. The Mott-Schottky and LSV curves demonstrate that CuPc act as a co-catalyst for water oxidation and a possible mechanism is proposed for water oxidation based on careful analysis of the detailed results. The holes from VB of TiO 2 photogenerated by electrons exciting are consumed by a process in which Cu 2+ is oxidized to Cu 3+ and Cu 4+ , and then oxidize water to produce oxygen. CuPc species is considered to be a fast redox mediator to reduce the activation energy of water oxidation in and effectively promote charge separation.