In this work, the nitrogen-doped TiO2 photocatalyst is synthesized and applied in a microfluidic all-vanadium photoelectrochemical cell for enhancing the solar energy storage. The use of the nitrogen-doped TiO2 photo-anode and the minimization design can ensure the visible-light response, increased specific surface area, vigorous pore structure and enhanced photon and mass transport as well as more uniform light distribution. Various characterizations are performed to evaluate the developed photocatalyst and microfluidic all-vanadium photoelectrochemical cell. The results confirm that the developed nitrogen-doped TiO2 photoanode can provide both the extended absorption spectrum and the small anatase crystal size as well as the obviously enlarged specific surface area with plentiful pore structure. Because of these merits, the microfluidic all-vanadium photoelectrochemical cell with the nitrogen-doped TiO2 photoanode yield the average photocurrent density of 0.103 mA/cm(2) during the long-term operation, which is much higher than those with the un-doped TiO2 photoanode (0.086 mA/cm(2)) and commercial P25 TiO2 photoanode (0.073 mA/cm(2)), presenting 19.8% and 41% improvements, respectively. The results demonstrate not only the promotion of the vanadium reversible redox pairs conversion but also the inherently excellent stability by the nitrogen-doped TiO2 photoanode.