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Rb3Si crystallizes in the hexagonal P6_3/mmc space group. The structure is one-dimensional and consists of two Rb3Si ribbons oriented in the (0, 0, 1) direction. Rb is bonded in a distorted water-like geometry to two equivalent Si atoms. Both Rb–Si bond lengths are 3.79 Å. Si is bonded in a 6-coordinate geometry to six equivalent Rb atoms.
RbSi crystallizes in the tetragonal I4_1/acd space group. The structure is three-dimensional. there are two inequivalent Rb sites. In the first Rb site, Rb is bonded in a 8-coordinate geometry to eight equivalent Si atoms. There are a spread of Rb–Si bond distances ranging from 3.65–3.84 Å. In the second Rb site, Rb is bonded in a 6-coordinate geometry to six equivalent Si atoms. There are a spread of Rb–Si bond distances ranging from 3.67–3.80 Å. Si is bonded in a 10-coordinate geometry to seven Rb and three equivalent Si atoms. There are two shorter (2.43 Å) and one longer (2.44 Å) Si–Si bond lengths.