Electronic states for two possible high-pressure phases (with the ThSi 2 structure and with the AlB 2 structure) of CaSi 2 are determined by means of a local density approximation band-structure calculation. We confirm that these polymorphs can be regarded as doped sp 2 networks of Si. However, a simple picture in terms of π-orbitals is not adequate for explaining the conduction bands, because (i) an s-like band, which is anti-bonding in sp 2 connections but bonding between segments of the network, appears and (ii) there is π -d hybridization between Si and Ca.