Shock synthesis of nanocrystalline Si, Ge and CdTe was accomplished using high- velocity thermal spray. Si or Ge powders were injected into a high energy flame, created by a thermal spray gun, where the particles melt and accelerate to impact on a substrate. The shock wave generated by the sudden impact of the droplets propagated through the underlying deposits, which induces a phase transition to a high pressure form. The decompression of the high-pressure phase results in the formation of several metastable phases, as evidenced by transmission electron microscopy and x-ray diffraction studies. The peak pressure is estimated to be ≈23GPa with a pulse duration of 1-5 ns. Transmission electron microscopy revealed that the metastable phases of Si with a size range of 2 to 5 nm were dispersed within Si-I. In Ge, a metastable phase, ST-12, was observed. This is a decompression product of Ge-II which possesses the β-Sn type of structure. In the case of CdTe, a fine dispersion of hexagonal CdTe particles, embedded in cubic-CdTe with an average size of 2 nm was obtained.