The plasma-spraying process generates materials with typical, porous and complex, microstructures. Inspired by Dielectric Multilayer Mirrors (DMMs), thermal sprayed media may be used in the field of optics, particularly for making scattering and reflecting coatings suitable for a large range of wavelengths. In fact, pores inside plasma sprayed matrix create numerous optical index discontinuities, similarly to the gaps created in DMMs, in order to obtain high reflectivity. The porosity of coatings microstructure can be customized by selection of plasma sprayed process parameters. This study aimed to optimize scattering and reflectance properties in porous alumina by the control of spray parameters resulting in the optimized porosity. A self-supporting bi-layer with a diffuse reflectance over 90% over a large band of wavelengths was obtained. The first layer (micro-structured), which is thick enough to support the free standing, was prepared by atmospheric plasma spraying (APS). The second layer (nanostructured) was manufactured by suspension plasma spraying (SPS) over the first layer in order to enhance the reflectance at short wavelengths.