Surface modification in ceramic/polymer composites holds paramount importance for electronic devices applications. Laser is a versatile and flexible device for modifying the surface characteristics of various materials. Here, we propose a novel approach to enhance the energy harvesting efficiency of polyvinylidene fluoride (PVDF) and zinc sulfide (ZnS) composite nanofibrous membranes through femtosecond laser surface modification. The electrospinning technique is used to produce nanofibers with a high β-phase content in a single step. The PVDF membrane was further enriched with ZnS nanoparticles to enhance the β-phase content. The membranes were systematically investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Electron Energy Loss spectroscopy (EELS), and Fourier-transform infrared spectroscopy (FTIR) to characterize their morphological and chemical properties. Femtosecond laser was employed to induce controlled surface modifications, resulting in hierarchical microstructures and surface functionalization. The results showed patterned tracks on the fiber surface while preserving its inherent nature. To validate its utility as an energy harvesting device, the membrane's capability was assessed by measuring the open circuit voltage. The results revealing average output voltages for nanogenerators treated with laser fluences of 0.5 J/cm2, 0.7 J/cm2, and 0.9 J/cm2 are 15.6 V, 25 V, and 17 V, respectively. The maximum output voltage is observed for a laser fluence of 0.7 J/cm2, attributed to the deeper structure created, increasing the surface area of contact and deformation in the structure. This work offers promising avenues for enhancing energy harvesting efficiency and expanding the scope of electronic devices such as sensors and actuators.