Carbon-fiber-reinforced silicon carbide composites (C/SiC) are promising materials for high temperature light weight structural components. However, a protective coating is necessary to prevent the oxidation of the carbon, especially at temperatures above 400 °C. Also the silica scale, which often forms on top of the C/SiC, must be protected from water vapor contact as the silica scale is not stable under these conditions. Hence, a protective coating, an Environmental Barrier Coating (EBC), is needed to shelter the material from the environmental influences of oxygen and water vapor. Current EBC systems employ multiple layers, each serving unique requirements. However, any mismatch in the coefficients of thermal expansion (CTE) leads to internal stress and results in crack formation. In this case, oxygen and water vapor penetrate through the EBC, reducing the lifetime of the component. Mullite (Al6Si2O13) is used in many known EBC systems on silicon-based ceramics either as an EBC itself or as a bondcoat. Due to its low CTE and its sufficient thermal cycling behaviour, mullite was chosen in this investigation as a first layer. As mullite suffers loss of SiO2 when exposed to water vapor at high temperatures, an additional protective top coat is needed to complete the EBC system. Different oxides were evaluated to serve as top coat, especially high temperature oxides with low coefficients of thermal expansion (LCTE). An Environmental Barrier Coating containing mullite as bondcoat and a LCTE oxide as a top coat is proposed. Both layers were applied via atmospheric plasma spraying. Results on the influence of processing conditions on the microstructure of single mullite and LCTE oxide layers and also mullite / LCTE oxide systems will be presented. Special emphasis was directed towards the crystallinity of the mullite layer, and in the top layer towards low porosity and reduced crack density.