Development of the binder-free electrode materials and employing in the supercapacitor is the essential footstep for high energy storage. Hence the present study highlights the cost-effective synthesis strategy for the binder-free growth of the amorphous polythiophene nanofibers over the nickel foam substrate. The presence of functional bonds like C=C, C-H, and C-S has confirmed the deposition of the polythiophene nanofibers on the nickel foam. While elemental analysis detected the uniform distribution of Carbon and Sulfur elements over nanofibers. The surface structure of the polythiophene is transformed from nanofibers to a wire-like structure as the result of the monomer concentration variation. The optimized polythiophene film exhibited the highest areal capacitance of 1263.2 mF/cm2 at 2mA/cm2 with 90.03% capacitance retention after 5000 cycles. Moreover, the aqueous asymmetric hybrid device (PTh//AC) is fabricated for real-time application which delivered 31.5F/g at 10mA/cm2. The highest specific energy of PTh//AC device was 6.3Wh/kg. Also, it showed good retention capability with 82.3% retention. Based on these results, the present investigation provides the performance metrics of the polythiophene nanofibers and highlights the potential utilization of the polythiophene-based supercapacitor in practical energy storage systems.