In this work, CdS/ZnO composite nanofibers (NFs) were prepared by the electrospinning of a sol-gel comprised of poly(caprolactone), zinc acetate dihydrate, cadmium acetate dihydrate, and ammonium sulfide. The electrospun NF mats were calcined under vacuum in an argon (Ar) atmosphere at 200 degrees C for 1 h. Standard physiochemical analysis techniques demonstrated the formation of the crystalline hexagonal phase of CdS and ZnO. Composite NFs showed good photocatalytic degradation of methylene blue (MB) dye under visible light irradiation compared to their counterparts. CdS nanoparticles, ZnO nanofibers, and composite NFs photodegraded 35.5%, 47.3%, and 90% of the MB dye, respectively, within 100 min. The reaction kinetics of MB photodegradation using the composite NFs followed the pseudo-first-order relation. Owing to their facile preparation and good photodegradation ability, the proposed method can be used to prepare various photocatalysts for wastewater treatment.