The adaption and inclusion of electrical technologies with various applications have motivated researchers to develop the most efficient and effective sensors, batteries and capacitors for safe, reliable and prolonged operations. However, miniaturization of sensors and practically associated with batteries and capacitors have driven them to employ nanofibers and nanotubes made of various material for reliable operations. Considering wide acceptance and available research for silicon material, nanofibers and nanoparticles made using silicon can be a great candidate for manufacturing of such sensors and electrical components. To employ nanofibers for those applications, understanding of its resistive characteristics can be crucial. In our study, we have manufactured hybrid silicon nanofibrous structure using novel approach of pico-second laser ablation and performed 4-point resistivity test to comprehend the change in its electrical behavior with variations in different laser parameters like frequency, power and scanning parameter of number of loops. Significant change in resistivity and topological structure was observed for surface ablated with various laser and scanning parameters.