This research investigates using CdS nanoparticles (NPs)-decorated ZnO nanofibers (NFs) as a novel photocatalytic for water splitting. For electrospinning, a colloidal solution, was used to prepare NFs, using a solution of zinc acetate dehydrate, cadmium acetate dehydrates, poly (e-caprolactone), and ammonium sulfide. The prepared NFs were calcinated under a low-temperature condition of 200 degrees C, a short time of 30 min, and an argon/hydrogen (Ar/H2) atmosphere. The use of the standard techniques led to the formation of crystalline CdS NPs-decorated ZnO NFs. Compared to native ZnO NFs and CdS NPs produced using similar conditions, the photocatalytic performance of the produced NFs was favorable regarding hydrogen production. For the composite NFs, native ZnO NFs, and CdS NPs, hydrogen evolution equaled approximately 820 mmolh-1 g-1, 115 mmolh-1 g-1, and 180 mmolh-1 g-1, respectively. The excellent photostability of the NFs may be related to the nanofibrous morphological sability to facilitate the transport of photocarriers and enhance the number of active sites on the surface of photocatalytic materials. The reported approach raises the potential for novel strategies to synthesize other NFs with innovative processes and the electrospinning technique.(c) 2022 THE AUTHORS. Published by Elsevier BV on behalf of Faculty of Engineering, Alexandria University. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/ licenses/by-nc-nd/4.0/).