By combining experimental techniques with ab initio density functional theory calculations, we describe the Si/Ag(111) 2D systems in terms of a sp2–sp3 form of silicon characterized by a vertically distorted honeycomb lattice provided by the constraint imposed by the substrate. The Raman spectrum reflects the multihybridized nature of the 2D Si nanosheets (NSs) resulting from a buckling-induced distortion of a purely sp2 hybridized structure. We show that vibrational and electronic properties of 2D Si-NSs are tightly linked to the buckling arrangement.