The lithium silanolate LiOSiMe3 is accessible from the reaction of Me3SiOSiMe3 with LiMe in tetrahydrofuran. Single crystals of [Li7(OSiMe3)7(THF)] were obtained from toluene at 25 °C. The structure of [Li7(OSiMe3)7(THF)] (C2/c) features a capped trigonal antiprismatic arrangement of seven Li atoms. The Li atoms in [Li7(OSiMe3)7(THF)] are μ3‐bridged by seven O atoms of the silanolate ligand.