Abstract: To further enhance the sensitivity of Cu/Ni materials for glucose detection, copper nitrate/nickel acetate composite polyvinylpyrrolidone (Cu(NO₃)₂/Ni(CH₃COO)₂/PVP@PVP) nanofibrous membranes were prepared by electrostatic spinning technique, dried, and finally calcined to obtain copper oxide composite nickel oxide nanofibers (CuO/NiO NFs) with hollow structure. The surface morphology, composition and structure of the hollow-structured CuO/NiO NFs materials were characterized by scanning electron microscopy, X-ray diffraction apparatus and X-ray photoelectron spectroscopy; and the effects of different ratios of hollow-structured CuO/NiO NFs on the electrocatalytic oxidation of glucose were investigated. The results demonstrate that the non-enzymatic glucose electrochemical sensor constructed with hollow-structured CuO/NiO NFs exhibits exceptional sensitivity (778.73 μA mmol/L ⁻¹ cm⁻²), a low detection limit (1.2 μmol/L), and a broad linear range (10 μmol/L to 13 mmol/L). Additionally, the sensor demonstrates satisfactory selectivity, repeatability, reproducibility, and long-term stability. This sensor provides a new design idea for the study of composite enzyme-free glucose sensing materials.