The phase transformations of Si under nanogrinding have been studied by transmission electron microscopy and Raman spectroscopy. Nanocrystalline high-pressure phases (Si-III/Si-XII) were found in the amorphous layer of the subsurface of heavily ground Si. The sequence of the phase transformation in nanogrinding has been found to be different to that in nanoindentation. The formation mechanism of the nanocrystalline high-pressure phases in nanogrinding is proposed based on experimental results.