An improved thermal barrier coating for metal substrates such as superalloys is disclosed. The coating is a slurry composition, comprising spheres of zirconia, at least some of which are hollow, contained within a porous oxide matrix, such as aluminosilicate. The slurry composition can be applied by slurry casting or similar techniques to the desired surface. Coating methods are also described. In general, they involve the application of successive layers of variations of the slurry composition, with various curing techniques used between layers and after the final coating is applied. Another embodiment of this invention embraces a composite coating, comprising (i) an oxide matrix phase; (ii) zirconia spheres embedded in the oxide matrix; and (iii) a porous phase.