In order to achieve better knowledge of the thermal barrier coatings (TBCs) by supersonic atmospheric plasma spraying (SAPS) process, an experimental study was carried out to elaborate the physicochemical properties of particles in-flight during the SAPS process. One type of commercially available agglomerated and sintered yttria-stabilized-zirconia (YSZ) powder was injected into the SAPS plasma jet and collected by the shock chilling method. The YSZ particles’ in-flight physicochemical properties during the SAPS process, including melting state, morphology, microstructure, particle size distribution, element composition changes, and phase transformation, have been systematically analyzed. The melting state, morphology, and microstructure of the collected particles were determined by scanning electron microscopy (SEM). The particle size distribution was measured by a laser diffraction particle size analyzer (LDPSA). Element compositions were quantitatively analyzed by an electron probe X-ray microanalyzer (EPMA). Additionally, the X-ray diffraction (XRD) method was used to analyze the phase transformation. The results showed that the original YSZ powder injected into the SAPS plasma jet was quickly heated and melted from the outer layer companied with breakup and collision-coalescence. The outer layer of the collected particles containing roughly hexagonal shaped grains exhibited a surface texture with high sphericity and the inside was dense with a hollow structure. The median particle size had decreased from 45.65 to 42.04 μm. In addition to this, phase transformation took place, and the content of the zirconium (Zr) and yttrium (Y) elements had decreased with the evaporation of ZrO2 and Y2O3.