The applicability of 2CaO·SiO2-CaO·ZrO2 ceramic coatings as thermal barrier coatings (TBCs) was investigated. Coatings consisting of various ratios of 2CaO·SiO2-CaO·ZrO2 bond-coated with NiCrAlY were prepared using the plasma spray process. The structure of the coatings was characterized by scanning electron microscopy and X-ray diffraction analysis. The resistance of the coatings to thermal shock was evaluated with acoustic emission techniques under a thermal cycle from 1273 K to room temperature, and the hot corrosion resistance of the coatings was investigated with V2O5 and Na2SO4 at 1273 K for 3 h. The 2CaO·SiO2-10~30mass%CaO·ZrO2 coatings had excellent thermal shock resistance, because the coatings contained a vertical micro-crack in a single flattened ceramic particle. These coatings possessed excellent corrosion protection preventing direct contact between the corrosive ashes and a NiCrAlY bond coating. The CaO in the coating reacted with vanadium compounds and inhibited the penetration of corrosive ashes to the bond coating. The developed 2CaO·SiO2-20mass%CaO·ZrO2 thermal barrier coating on stationary vanes was evaluated in an actual gas turbine. The ceramic coating did not separate from the bond coating and reacted with SOx in combustion gas to produce a stable sulfate (CaSO4), which fixed in the coating. The TBC effectively protected the metal substrate of the vanes in practical operating condition for 25,000 h.