A novel plasma spray process for producing nanostructured coatings, hypersonic plasma particle deposition (HPPD), has been experimentally investigated. In HPPD, vapor phase precursors are injected into a plasma stream generated by a DC arc. The plasma is quenched by supersonic expansion through a nozzle into a vacuum (~ 2 torr) deposition chamber. Ultrafine particles nucleated in the nozzle are accelerated in the hypersonic free jet downstream of the nozzle and inertially deposited onto a substrate. The short transit times between the nozzle and the substrate (< 50 μs) prevent inflight agglomeration, while the high particle deposition velocities result in the formation of a consolidated coating. We have investigated the production of silicon and silicon carbide coatings using SiCl4 and CH4 precursors. Silicon deposits analyzed by transmission electron microscopy were found to have nanostructured regions with grain sizes varying from 5-20 nm. Corresponding particle size distributions measured before deposition using an extractive aerosol probe peaked around 15 nm, suggesting negligible grain growth occurred in the samples studied. Silicon carbide particle size distributions measured at various deposition chamber pressures verify that the low residence time characteristic of the HPPD process minimizes in-flight agglomeration.