Plasma spraying was used to deposit Li3PO4 coatings from sintered dense powders in three size ranges to study the effects of particle size and spraying distance. Coating microstructure, crystal structure, and composition were characterized using SEM, XRD, ICP-MS, and FTIR. It was found that sintered dense powders have a high temperature orthorhombic phase (γ-Li3PO4) that differs from the β-Li3PO4 phase associated with agglomerated Li3PO4. Plasma-sprayed coatings produced from these powders have similarly dense microstructures with fracture-surface morphology like that of sintered bulk. The effect of particle size and spraying distance on atomic ratio is also investigated in the study.