Suspension plasma spraying (SPS) is able to process a stabilized suspension of nanometer-sized feedstock particles to form thin (from 20 to 100 µm) coatings with unique microstructures. The void network architecture of these ceramic coatings is a challenge to be characterized and quantified using commonly used techniques due to small sizes involved. Nevertheless, the discrimination of these pore architectures in terms of size and shape distribution, anisotropy, specific surface area, etc., is critical for the understanding of processing, microstructure, and properties relationships. USAXS (Ultra-Small Angle X-Rays Scattering) appeared as a suitable measurement technique allowing discriminating the void size distribution over a large range (up to four orders of magnitude). Results indicate that as-sprayed SPS coatings exhibit unusual porous architecture: 1) average void size is about the same than the feedstock one; i.e., nanometer sizes with multimodal void size distribution; 2) about 80% of the voids exhibit characteristic dimensions smaller than 30 nm; 3) the total void content varies between 13 to 20% depending upon considered operating parameters. In-situ annealing measurements were performed as they proved to deliver more relevant results compared to ex-situ measurements: even at temperatures as low as 800°C, the microstructure transforms - while the total void content does not change significantly. Indeed, it has been demonstrated that the smallest voids (equivalent diameters smaller than 50 nm) coalescence was the predominant mechanism and that it was more sensitive to temperature than time.