<p>Polyvinylidene fluoride (PVDF) combined with <i>N</i>,<i>N</i>-dimethylformamide (DMF) is a promising material for supercapacitor electrodes due to its chemical stability and favorable electrochemical properties. In this study, electrospinning-assisted coating, spray coating, and slurry deposition were comparatively evaluated for DMF/PVDF-based electrodes. Spray-coated PVDF electrodes exhibited the highest specific capacitance (588.56 F g⁻¹ at 1 A g⁻¹) but poor cycling stability (13.39% retention after 10,000 cycles at 20 A g⁻¹). Slurry-deposited electrodes showed balanced performance with 476.9 F g⁻¹ at 1 A g⁻¹ and 52.85% retention after 500 cycles at 10 A g⁻¹. Electrospinning-coated PVDF electrodes delivered lower capacitance (154.48 F g⁻¹ at 1 A g⁻¹) while maintaining moderate stability (48.07% retention after 10,000 cycles at 15 A g⁻¹). These results demonstrate that the electrode fabrication technique plays a decisive role in optimizing the electrochemical performance and durability of PVDF-based supercapacitor electrodes.</p>