Cu(0) nanoparticles supported on TiO2 nanofibers (Cu-decorated TiO2 NFs) are introduced as an effective photocatalyst for hydrolytic dehydrogenation of ammonia borane (AB) under solar radiation. The introduced Cu-decorated TiO2 NFs were prepared using electrospinning followed by hydrothermal treatment as a novel route for preparation of metal-decorated metal oxide nanofibers. Interestingly, the utilized physicochemical characterizations showed that the prepared nanocatalyst composed of core TiO2 NFs decorated by Cu(0) NPs. A strong photocatalytic activity for catalytic hydrolysis of AB under solar radiation using the introduced nanocatalysts was observed. The results reveal that high rate of hydrogen release from ammonia borane (2.75 equivalent moles) as compared to undecorated TiO2 NFs (1.6 equivalent moles) and pristine Cu NPs (1.2 equivalent moles). The obtained high hydrogen production, in case of the introduced Cu-decorated TiO2 NFs, is attributed to the dual effect of counter parts. Furthermore, the introduced nanofibers could be utilized for three successive cycles with the same efficiency which reflects high stability. Moreover, the photocatalytic activity of the introduced NFs was further confirmed by photodegradation of methylene blue (MB) under solar radiation; complete removal was observed after 120 min. (C) 2015 Elsevier B.V. All rights reserved.