Thermal spraying enables a fast and effective way to additively deposit various ceramics as electric insulators, which are used in conditions where polymers are not suitable. Alumina (Al2O3) is among the most widely employed materials in the coating industry because it exhibits good dielectric properties, high hardness, and high melting point, while still being cost-effective. Various parameters (e.g., feedstock type, plasma gas mixture, plasma power) significantly influence the resulting coating in terms of microstructure, porosity, crystallinity, and degree of unmolten and molten particles. As a consequence, these parameters need to be investigated to estimate their impact on the electrical insulating properties of thermally sprayed alumina. This study focuses on the development of a novel electric insulation coating from Al2O3 feedstock powders deposited via atmospheric plasma spray (APS). The microstructure, porosity, and corresponding crystallographic phases have been analyzed with optical microscopy, XRD, and SEM images. To achieve an understanding of the parameters influencing the electrical insulation performance of the manufactured coatings, an in-depth analysis of the fundamental dielectric parameters (e.g., DC resistance, breakdown strength, dielectric loss tangent, and permittivity) is presented.