A worm-like oxide Ca₃Co₂O₆ was prepared by electrostatic spinning as a cathode material for solid-oxide fuel cells. Compared to the plain granular structure, the worm-like Ca₃Co₂O₆ exhibits a desirable morphological organization and an enhanced electrochemical performance. At 1073 K, polarization resistance with the worm-like cathode is favorably reduced to 0.151 Ω cm², and the power peak of the corresponding single cell reaches to 512 mW cm⁻², showing a fast cathodic kinetics. By contrast, the polarization resistance with the plain cathode is 0.275 Ω cm², and the power peak of the corresponding single cell is 406 mW cm⁻². Under a constant voltage load of applied 0.6 V at 1023 K, cell power with the worm-like cathode maintains steadily from 420 to 400 mW cm⁻² after 14 h of running time, showing a less fading rate, a more stable performance, and a better application prospect than the plain cathode.