In the present study, we introduce Poly(vinylidene fluoride) (PVDF) nanofibers containing nickel (Ni) nanoparticles (NPs) as a result of an electrospinning. Typically, a colloidal solution consisting of PVDF/Ni NPs was prepared to produce nanofibers embedded with solid NPs by electrospinning process. The resultant nanostructures were studied by SEM analyses, which confirmed well oriented nanofibers and good dispersion of Ni NPs over them. The XRD results demonstrated well crystalline feature of PVDF and Ni in the obtained nanostructures. Physiochemical aspects of prepared nano-structures were characterized for TEM which confirmed nanofibers were well-oriented and had good dispersion of Ni NPs. Furthermore, the prepared nano-structures were studied for hydrogen production applications. Due to high surface to volume ratio of nanofibers form than the thin film ones, there was tremendous increase in the rate of hydrogen production. Overall, results satisfactorily confirmed the use of these materials in hydrogen production.