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The judicious design of highly electrochemically active materials on 1D fiber substrate to form a hierarchical integrated hybrid structure is an efficient technique to improve the limited cylindrical space and volumetric energy density of fiber‐shaped supercapacitors (FSCs). Herein, a 3D negative electrode, consisting of vertically aligned interconnected mesoporous Co‐N/C leaf‐like structure on 1D MXene‐carbon fiber (Co‐N/C@MX/CF) is prepared by controlling the composition and morphology. At the same time, a 3D positive electrode is also prepared by introducing Mo in NiCo‐LDH anchored on Co‐N/C@MX/CF (Mo‐NiCo‐LDH@Co‐N/C@MX/CF) by electrodeposition method. Benefitting from the systematic hierarchical structures with highly accessible surface area, adequate pore size and easy permeation of electrolyte, both positive and negative electrodes demonstrate highly improved electrochemical performance with areal capacity/capacitance of 0.96 mAh cm−2/4.55 mF cm−2 at a current density of 3.86 mA cm−2, respectively. Furthermore, the fiber‐shaped solid‐state hybrid supercapacitor (FSHSC) based on Mo1.5NiCo‐LDH@Co‐N/C@MX/CF(+)//Co‐N/C0.5@MX/CF(−) is fabricated, exhibiting compelling energy density of 86.72 mWh cm−3 at a power density of 480.30 mW cm−3 with an outstanding capacitance retention of 80.2% after 20000 galvanostatic‐charge‐discharge cycles. This study puts forward a new perspective on the development of highly efficient FSCs for practical application.