Calcium magnesium alumina-silicate (CMAS) corrosion on thermal barrier coatings (TBCs) is one of the reasons for the early delamination of TBCs. In this study, the effects of CMAS on the microstructure evolution of TBCs were investigated for yttria-stabilized zirconia (YSZ), lanthanum zirconate (LZ), and composite coating with a 50:50 volume ratio of LZ and YSZ (LZ-YSZ). The LZ showed the mitigated penetration of CMAS by the formation of the reaction products produced by the high reactivity between the LZ and the molten CMAS. The LZ-YSZ showed a denser microstructure on the surface, resulting in retarding the penetration of CMAS. Therefore, the LZ-YSZ composite TBC is expected to prolong the lifetime performance and protect against further corrosive degradation of TBCs in high-temperature environments. The infiltration behavior and reaction mechanism of molten CMAS were discussed based on the microstructures after the corrosion test.