Pulsed Laser Deposition (PLD) allows the ablation of nonconductive and high melting point target materials and the preparation of films with complex composition. High energy impact leads to melting and evaporation of the target material in a single step. In case of mullite ablation, the flux of the metal components is stoichiometric. Under reduced pressure the oxygen content in the layers decreases. However, after a short oxidation treatment, the formation of mullite in the coating is completed, as confirmed by IR spectroscopy and XRD investigations. For a commercial Si-SiC precoated C/C material, the effectiveness of additional PLD mullite layers as outer oxidation protection is tested in the temperature range 773 K < T < 1873 K. Mullite coatings with a thickness of 2.5 pm improve the oxidation behaviour significantly. Because of SiO2 formation at the mullite-SiC interface, all samples exhibited a mass increase upon oxidation. For oxidation durations of three days, only amorphous SiO2 is formed at the mullite-SiC interface. The inward diffusion of oxygen across the outer mullite-containing layer controls the kinetics of the reaction, as was deduced from 18O diffusivity measurements in PLD mullite layers. At temperatures close to the eutectic temperature (1860 K), mullite can seal defects. The calculated oxidation rates resulting from the diffusion parameters in SiO2 and mullite are close to the thermogravimetric data.