Chromium carbide-nickel chromium coatings produced by HVOF spraying are widely used for high temperature wear and erosion resistant applications. Examination of the literature shows that whilst the mechanical properties of these coatings have been widely investigated, there has been little research into the physical processes occurring during HVOF spraying of this system, such as carbide dissolution, liquid-metallic phase oxidation, decarburisation and rapid solidification. The purpose of the present work has been to perform a systematic characterisation of the chromium carbide-nickel chromium system in both the initial powder and as-sprayed states with a variety of spraying conditions using optical, scanning and transmission electron microscopy, electron microprobe and X-ray diffraction. The presence of amorphous and nanocrystalline phases has been demonstrated. The nanocrystalline structures tend to be Ni rich, with the amorphous phases rich in Cr. Carbides of the form Cr3C2 were found to be dissolved slightly during spraying, increasing the Cr and C contents of the liquid metallic phase. There was no evidence of chromium carbide oxidation.