Treatment of the phenyl-substituted silane 4 with lithium metal afforded the functionalized lithiosilane rac-2 by selective cleavage of one Si−C bond between silicon and a phenyl group. The resulting lithiosilane rac-2 crystallizes as the dimer (2·THF)2, which represents the first example of a dimeric organyl-substituted lithiosilane in the presence of THF.