Environmental degradation of thermal barrier coatings (TBC) by molten deposits such as calcium magnesium alumino-silicates (CMAS) is one of the most vital factors resulting in the failure of thermal barrier coatings, while turbine engine inlet temperatures are kept increasing for higher fuel efficiency. A new phase composite ceramic had been developed and evaluated for the topcoat of a durable thermal barrier coating (TBC) system with low thermal conductivity property and improved erosion resistance. The present work is to continue the effort to exploring the behavior of CMAS resistance of the phase composite TBC at high temperatures. The effects of CMAS attack and thermal exposure on the TBC degradation were investigated in experimental runs. In addition, a YAG-modified layer over the top of the TBC was applied with the attempt to improve CMAS resistance of the TBC system. The evaluation of CMAS resistance was focused on the most important characteristics of coating microstructure, CMAS penetration, and failure mode and test condition factors. The mechanisms for the CMAS infiltration and the TBC damages were discussed based on the analyses of the CMAS corroded samples in details.