An intermediate temperature solid oxide fuel cell (SOFC) electrolyte film of La0.8Sr 0.2Ga0.8Mg0.2O2.8 (LSGM) was fabricated using a plasma spray process. The microstructure and phase were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical behavior of the thermal sprayed LSGM film was investigated using electrochemical impedance spectroscopy (EIS). The study indicates that thermal spray can deposit a dense LSGM layer. It was found that the rapid cooling in the thermal process led to an amorphous or poor crystalline LSGM deposited layer. This amorphous structure has a significant effect on the performance of the cell. Crystallization of the deposited LSGM layer was observed during annealing between 500–600 °C. After annealing at 800 °C, the ionic conductivity of the sprayed LSGM layer can reach the same level as that of the sintered LSGM.