Using CVD, compositionally graded coatings of mullite (3 Al 2 O 3´2 SiO 2 ) and alumina (Al 2 O 3 ) were deposited on Si-coated substrates from mixtures of silicon tetrachloride, aluminum trichloride, carbon dioxide, and hydrogen. The coatings were compositionally graded, with the Al/Si ratio increasing towards the outer layer of the coatings. The preparation of the coatings was carried out in a vertical, hot-wall CVD reactor. The results of previous experimental studies on the deposition of aluminosilicate species have been used to identify operating conditions where deposition of coatings with alumina content equal to, or greater than, that corresponding to stoichiometric mullite was possible. The scheme for the preparation of the graded mullite/alumina coatings was based on utilizing the positive effect of decreasing the residence time of the reactive mixture in the reactor, and of increasing the Al/Si ratio in the feed on the incorporation of Al 2 O 3 in the deposit.