The controllable photocatalytic hydrolysis of alkali-metal borohydrides is studied for hydrogen generation in this work. The results indicate that the photocatalysis of P25 TiO2 controllably promotes the hydrogen generation rates from alkali-metal borohydride hydrolysis. Its apparent activation energy is calculated to be reduced from 57.20 to 53.86kJmol(-1). This is due to the mechanism of photocatalytic hydrolysis: holes (h(+)) react with BH4- and OH- to form H-2 and B(OH)(4)-, meanwhile electrons (e(-)) react with H+ to from H-2. In addition, Ti3+-doped TiO2 with a crystalline-disordered core-shell structure can be generated during the photocatalytic hydrolysis process. The consumption of e(-) is identified as the rate-limiting step in photocatalytic hydrolysis process. Copyright (c) 2017 John Wiley & Sons, Ltd.