Manganese-cobaltite spinel coatings were produced on Fe-Cr alloys for the improvement of the chemical and mechanical stability of solid oxide fuel cell (SOFC) interconnects. It was found by thermal investigation, i.e., the microscopy of various samples that were heat-treated in air at 800 °C, that the screen-printed coating more effectively inhibited oxide scale growth than the sputtered coating. The reason why the manufacturing method of the spinel coating affected the oxide scale growth rate was investigated. It was demonstrated that the oxide scale in both the samples after annealing in air at 800 °C for 5000 h comprised MnCr2O4 and Cr2O3 with no difference in composition. However, the interface between the alloy and the oxide scale was deeper and rougher and had a larger grain size because of the high oxygen diffusivity in the sputtered coating. In contrast, in the screen-printed sample, the dense spinel layer above the oxide scale blocked oxygen diffusion into the alloy, so the oxide scale growth rate was lower and the interface between the alloy and oxide scale remained flat even after thermal treatment. Introducing a reduction treatment in the manufacturing process made the Mn-Co spinel layer denser and further inhibited the oxide scale growth. Moreover, the addition of Li as a sintering aid into the Mn-Co spinel was found to even more effectively inhibit the oxide scale growth.