Abstract Electrolyte-free fuel cell (EFFC) which holds the similar function with the traditional solid oxide fuel cell (SOFC) but possesses a completely different structure, has draw much attention during these years. Herein, we report a complex of MZSDC–LNCS (Mg 0.4 Zn 0.6 O/Ce 0.8 Sm 0.2 O 2− δ –Li 0.3 Ni 0.6 Cu 0.07 Sr 0.03 O 2− δ ) for EFFC that demonstrates a high electrochemical power output of about 600 mW cm −2 at 630 °C. The co-doped MZSDC is synthesized by a co-precipitation method. Semiconductor material of LNCS is synthesized by direct solid state reaction. The microstructure and morphology of the composite materials are characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy-dispersive X-ray spectrometer (EDS). The performance of the cell with a large size (6 × 6 cm 2 ) is comparable or even better than that of the conventional solid oxide fuel cells with large sizes. The maximum power output of 9.28 W is obtained from the large-size cell at 600 °C. This paper develops a new functional nanocomposite for EFFC which is conducive to its commercial use.