With the increasing importance of energy storage technologies, the demand for supercapacitors combining high energy density with fast reversible rechargeability is increasing. However, conventional multistep synthesis methods increase the production costs and limit the practical application of these technologies. To solve this problem, we developed two innovative electrodes, UiO-66/PVDF/PGE and metal-organic framework (MOF)-199/PVDF/PGE. These electrodes produced with a one-step electrospinning technique provide a cost-effective solution by simplifying the fabrication process and reducing costs. The successful incorporation of MOFs into the polymer matrix was confirmed by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) analyses, and a homogeneous nanofiber morphology was observed by scanning electron microscope (SEM) imaging. Thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) analyses showed significant improvements in the thermal and structural stability of the composites. The electrochemical properties were analyzed in detail by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods. The electrospun UiO-66/PVDF/PGE electrode demonstrated a high specific capacitance of 1619.26 F/g with exceptional cycling performance at 1 A/g current density, while the MOF-199/PVDF/PGE electrode achieved a value of 933.19 F/g. Both electrodes maintained 99.16 and 102.04% of their initial capacitance after 3000 cycles, respectively, exhibiting outstanding stability for long-term energy storage applications. These results demonstrate that UiO-66/PVDF/PGE and MOF-199/PVDF/PGE are promising as scalable, high-performance, and cost-effective electrode materials for supercapacitor technologies.