The evolution of Co coating in solid oxide fuel cells (SOFCs) under low and medium temperatures (<700 °C) is different from that under high temperatures. In this context, the oxidation corrosion of 441 ferritic stainless steel (FSS) with a Co coating in air under 650 °C was investigated. The results indicated that the Co coating was oxidized rapidly and a Co3O4 spinel layer formed in the initial exposure of 5 min, which improved the oxidation resistance of 441 steel. After oxidation at 650 °C for 120 h, a Cr2O3 layer with a thickness of 0.2–0.4 μm was observed on the surface of bare 441 steel, while the surface oxide scale of Co-coated 441 steel samples was composed of an inner Cr2O3 and Fe2O3 solid solution (0.1–0.3 μm thick), an intermediate (Fe, Co)3O4 layer and an outer Co3O4 spinel layer, respectively. The Co-coated 441 steel sample exhibited better electrical properties. After oxidation at 650 °C for 120 h, the area-specific resistance (ASR) of the Co-coated steel was 3.73 mΩ·cm2, which was 25.4% lower than that of bare 441 steel as 5 mΩ·cm2. Furthermore, the thermal growth process and protection mechanism of Co coating at 650 °C were discussed.