We have demonstrated herein a simple method for the fabrication of hierarchical structure of ZnO enriched fibrous PVA membrane. The observed result has shown the uniform coating of ZnO on the fiber surface. Effective control of the density of coating has been brought about by changing the concentration of ZnO and combined sol-gel coating. Serving as seeds for the growth of nanorods, the ZnO nuclei evolve to form nanorods whose density and length have been controlled by thermal treatment. We believe that the methodology described in this report offers a simple and straightforward route to prepare the hybrid structure and furthermore find an exercise in various optoelectronic fields.