Next-generation energy storage devices require electrodes that combine high charge storage capacity, mechanical robustness, and scalable fabrication. Here, we present a new class of thermally stabilized, hierarchically porous hybrid fibers integrating copper benzene tricarboxylate (Cu-BTC) metal-organic frameworks (MOFs) with liquid crystalline graphene oxide, addressing long-standing challenges in MOF processing for fiber-based architectures. Incorporating Keggin-type phosphotungstic acid polyoxometalate enhances the thermal stability of the Cu-BTC framework, enabling wet spinning and thermal reduction to produce conductive MOF–reduced graphene oxide hybrid fibers. In addition to providing high surface area and hierarchical porosity, the MOF structure introduces redox-active sites that contribute to pseudocapacitance, further improving charge storage. The resulting fibers exhibit outstanding electrochemical performance in a symmetric two-electrode configuration, delivering a gravimetric capacitance of 476.9 F g⁻¹ at 0.77 A g⁻¹ and excellent cycling stability (96.7% retention over 4000 cycles). Beyond electrochemical function, the fibers demonstrate exceptional mechanical strength (Young’s modulus >42 GPa), offering a rare combination of durability and performance. This work establishes a versatile platform for integrating MOFs into flexible, high-performance, and scalable fiber-based energy storage devices.