The electronic structures of lithium metasilicate (${\mathrm{Li}}_{2}$${\mathrm{SiO}}_{3}$) and lithium disilicate (${\mathrm{Li}}_{2}$${\mathrm{Si}}_{2}$${\mathrm{O}}_{5}$) are calculated using a first-principles orthogonalized linear combination of atomic-orbitals method. Results are compared with experimental x-ray-photoemission spectra and earlier calculations on sodium metasilicate and sodium disilicates.