A technique used to improve the life cycle and/or the working temperature of the turbine blades uses ceramic coatings over metallic material applied by electron beam-physical vapor deposition (EB-PVD). The most usual material for this application is yttria doped zirconia. Addition of niobia, as a co-dopant in the Y 2O 3–ZrO 2 system, can reduce thermal conductivity. The purpose of this work is to evaluate the influence of the addition of niobia on the microstructure and thermal properties of the ceramic coatings. This new formulation will, in the future, be able to become an alternative to the composition currently used by the aerospace field in EB-PVD thermal barrier coatings (TBC). A significant reduction of the thermal conductivity, measured by laser flash technique, in the zirconia ceramic coatings co-doped with yttria and niobia when compared with zirconia–yttria coatings was observed.