Advanced ceramic materials of perovskite structure have been developed for potential application in thermal barrier coating systems, in an effort to improve the properties of the pre-existing ones like yttria stabilized zirconia. Yb 2 O 3 and Gd 2 O 3 doped strontium zirconate (SrZrO 3 ) and barium magnesium tantalate (Ba(Mg 1/3 Ta 2/3 )O 3 ) of the ABO 3 and complex A(B’ 1/3 B” 2/3 )O 3 systems respectively, have been synthesized using ball milling prior to solid state sintering. Thermal and mechanical investigations show desirable properties for high temperature coating applications. On atmospheric plasma spraying, the newly developed TBCs reveal promising thermal cycle lifetime above 1300°C.