The microstructures of thick plasma-sprayed yttria-stabilized zirconia (8% mass fraction yttria) deposits were studied in a series of Porod small-angle neutron scattering (SANS) and multiple small-angle neutron scattering (MSANS) experiments. Three main void components were identified in the deposits: intrasplat cracks, interlamellar planar pores, and globular pores. The SANS and MSANS measurements were analyzed using the traditional theory for Porod scattering and a recently developed three-component model for MSANS evaluation. The average size, volume fraction, internal surface area, and orientation distribution for each void component within the deposits were determined. This study focused on gaining a better understanding of the effects of initial feedstock particle size and annealing temperatures on the microstructure of deposits sprayed under equivalent particle-impact conditions. Quantitative results are presented for each of four deposit samples: one prepared using the as-received feedstock particle wide-size distribution and three prepared from feedstock powder of different and relatively narrow particle size ranges with average sizes of 32, 47, and 88 μm. Except for the coarse (88 μm) feedstock powder, only mild monotonic variations were found in the microstructural anisotropies, the porosities (13 ± 1%), and the internal surface areas in the as-sprayed deposits. The internal surface area was independent of the feedstock particle size, even with the coarse feedstock. When the deposits were annealed at high temperatures (1100 and 1400 °C), the microstructures were altered with a reduction of the total internal surface area and a mild coarsening of the voids. These changes in the microstructural evolution were well-captured and described by the three-component model. The results were compared and related with those obtained from scanning electron microscopy images and elastic moduli measurements.