The anode of an alkaline electrolytic cell for water electrolysis was modified by TiO2 photocatalysts with different morphologies. The water electrolysis was coupled with photocatalytic decomposition of water by irradiation of UV light on the modified anode. And a feasible process for the hydrogen production of water electrolysis assisted by photocatalysis (WEAP) was proposed and experimentally confirmed. The results show that the highly ordered, vertically oriented tubular arrays structure on Ni anode surface has better hydrogen production performance than random TiO2. In WEAP process, the maximum rate of hydrogen production is 2.77 ml/(h*cm(2)) when the anode modified by ordered TiO2 nanotube arrays, compared to traditional alkaline electrolytic cell for water electrolysis with Ni anode, H-2-production rate increased by 139%. (c) 2012 Elsevier B.V. All rights reserved.