A heterostructured molybdenum disulfide@vertically aligned graphene fiber (MoS₂@VA-GF) is developed for high electrochemical capacitance. The MoS₂ nanosheets are uniformly decorated on vertical graphene fibers via C–O–Mo covalent bonds. The unique vertical-aligned structure, large faradic activity, in situ interfacial connectivity, and high-exposed surface/porosity create efficient ionic pathways, interfacial electron mobility, and pseudocapacitive accessibility, accelerating charge transport and intercalation/de-intercalation. The MoS₂@VA-GF exhibits a high gravimetric capacitance of 564 F g⁻¹ in 1 M H₂SO₄ electrolyte. The MoS₂@VA-GF-based solid-state supercapacitors deliver high energy density (45.57 Wh kg⁻¹), good cycling stability (20,000 cycles), and deformable/temperature-tolerant capability. These supercapacitors can power multicolored optical fiber lamps, wearable watches, electric fans, and sunflower toys. The study highlights the importance of ordered structures and high electrochemical activities in fiber-shaped electrochemical supercapacitors (FESC). The key challenges in FESC include low energy density compared to flexible batteries, which is addressed by designing fiber electrodes with ordered structures, large specific surface areas, engineered porosities, and high electrochemical activities. Two-dimensional nanomaterials, such as graphene and MXene, are promising candidates for FESC electrodes due to their large specific surface areas, tailored porous backbones, anisotropic frameworks, high electrical conductivity, and strong interlayer van der Waals effects. MoS₂, a 2D transition metal dichalcogenide, is a promising candidate for FESC due to its high theoretical capacitance, large and controllable structures, and high electrochemical activity. The MoS₂@VA-GF-based supercapacitors demonstrate excellent energy storage performance, with high energy density, good cycling stability, and deformable/temperature-tolerant capabilities. These findings offer a powerful platform for architecting highly ordered and multifunctional fiber electrodes for new-generation smart textile energy storage and wearable industry.A heterostructured molybdenum disulfide@vertically aligned graphene fiber (MoS₂@VA-GF) is developed for high electrochemical capacitance. The MoS₂ nanosheets are uniformly decorated on vertical graphene fibers via C–O–Mo covalent bonds. The unique vertical-aligned structure, large faradic activity, in situ interfacial connectivity, and high-exposed surface/porosity create efficient ionic pathways, interfacial electron mobility, and pseudocapacitive accessibility, accelerating charge transport and intercalation/de-intercalation. The MoS₂@VA-GF exhibits a high gravimetric capacitance of 564 F g⁻¹ in 1 M H₂SO₄ electrolyte. The MoS₂@VA-GF-based solid-state supercapacitors deliver high energy density (45.57 Wh kg⁻¹), good cycling stability (20,000 cycles), and deformable/temperature-tolerant capability. These supercapacitors can power multicolored optical fiber lamps, wearable watches, electric fans, and sunflower toys. The study highlights the importance of ordered structures and high electrochemical activities in fiber-shaped electrochemical supercapacitors (FESC). The key challenges in FESC include low energy density compared to flexible batteries, which is addressed by designing fiber electrodes with ordered structures, large specific surface areas, engineered porosities, and high electrochemical activities. Two-dimensional nanomaterials, such as graphene and MXene, are promising candidates for FESC electrodes due to their large specific surface areas, tailored porous backbones, anisotropic frameworks, high electrical conductivity, and strong interlayer van der Waals effects. MoS₂, a 2D transition metal dichalcogenide, is a promising candidate for FESC due to its high theoretical capacitance, large and controllable structures, and high electrochemical activity. The MoS₂@VA-GF-based supercapacitors demonstrate excellent energy storage performance, with high energy density, good cycling stability, and deformable/temperature-tolerant capabilities. These findings offer a powerful platform for architecting highly ordered and multifunctional fiber electrodes for new-generation smart textile energy storage and wearable industry.