In this study we present a new fabrication approach to obtain enhanced surface-to-volume ratio and porous-fibrous morphology composite material zinc oxide-cellulose acetate butyrate (CAB). The new approach consist on using zinc oxide nanoparticles that are embedded in CAB microfiber mats obtained by electrospinning followed by ZnO nanoparticles growth by a hydrothermal method. The resulting composite material has a much higher active surface that contributes to enhanced photocatalytic activity. The photocatalytic activity of CAB-ZnO composites obtained by our procedure was assessed over Rhodamine B and basic fuchsine and was found to be higher by about 40% compared to the composite obtained by the dipping technique. The composite materials microscopy, structural and compositional characterizations confirm the enhanced surface-to-volume ratio and porous-fibrous morphology compared with CAB-ZnO composites prepared by dip method.