In this study, Ni-doped titanium dioxide (TiO2) electrospun nanofibers are introduced as novel material for dehydrogenation of ammonia borane (AB) complex. Hydrolysis experiments with introduced catalytic nanofibers are prevailed to rapidly release hydrogen from AB complex. Typically, Ni nanoparticles (NPs) behave as a catalyst, meanwhile the incorporation of nickel NPs lead to decrease in the electrons/holes recombination rate in TiO2 which resulted in the increase of active ions in the solution to a rapid evolution of hydrogen gas at room temperature. The utilized physiochemical analyses indicate that the introduced Ni-doped TiO2 nanofibers have a smooth surface and uniform diameters along their lengths. Under sunlight irradiation, the hydrogen production rate in case of utilizing Ni-doped TiO2 nanofibers is rapidly increased compared to the pristine TiO2 nanofibers, the maximum hydrogen equivalent in case of the doped nanofibers is 2.6 while the pristine one is 1.4. Both formulations exhibit almost equal low activity in daylight as the observed hydrogen equivalent is 0.4. Overall, this study proposes cheap, stable and effective material for AB dehydrogenation at room temperature. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.