Abstract: The high-pressure behaviour of NaSi has been studied using Raman spectroscopy and angle-dispersive synchrotron X-ray diffraction to observe the onset of structural phase transformations and potential oligomerisation into anionic Si nanoclusters with extended dimensionality. Our studies reveal a first structural transformation occurring at 8–10GPa, followed by irreversible amorphisation above 15GPa, suggesting the formation of Si–Si bonds with oxidation of the Si− species and reduction of Na+ to metallic sodium. We have combined our experimental studies with DFT calculations to assist in the analysis of the structural behaviour of NaSi at high pressure. [Copyright &y& Elsevier]