Photoelectrochemical (PEC) water splitting has been considered as a promising and environmentally benign approach for efficient and economic hydrogen generation by utilization of solar energy. Development of semiconductor materials with low band gap, high photoelectrochemical activity and stability has been of particular interest for a viable PEC water splitting system. In this study, Co doped ZnO, (Zn0.95Co0.05)O nanowires (NWs) was selected as the composition for further co-doping with nitrogen by comparing solar to hydrogen efficiency (SHE) of ZnO NWs with that of various compositions of (Zn1-xCox)O NWs (x = 0, 0.05, 0.1). Furthermore, nanostructured vertically aligned Co and N-doped ZnO, (Zn1-xCox)O:N NWs (x = 0.05) have been studied as photoanodes for PEC water splitting. An optimal SHE of 1.39% the highest reported so far to the best of our knowledge for ZnO based photoanodes was obtained for the co-doped NWs, (Zn0.95Co0.05)O:N - 600 NWs generated at 600 degrees C in ammonia atmosphere. Further, (Zn0.95Co0.05)O:N-600 NWs exhibited excellent photoelectrochemical stability under illumination compared to pure ZnO NWs. These promising results suggest the potential of (Zn0.95Co0.05) 0:N-600 NWs as a viable photoanode in PEC water splitting cell. Additionally, theoretical first principles