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A high-performance fiber-shaped electrode composed of hierarchical NiCo2O4@polypyrrole core–shell nanowires on hemp-derived carbon (HDC) microfiber is successfully fabricated, which takes advantage of the high electrical conductivity of polypyrrole and carbon microfiber to boost the pseudocapacitive performance. The as-synthesized electrode exhibits an ultrahigh specific capacitance of 2055 F g−1, excellent rate performance and outstanding cycling stability (90% capacity retention over 5000 cycles). Based on the good mechanical flexibility and stability of the HDC, a fiber-shaped all-solid-state symmetric supercapacitor is designed which demonstrates a high energy density of 17.5 W h kg−1 at a power density of 500 W kg−1, good stability over 10 000 cycles and high physical flexibility.