The reaction of aryl-substituted disilanes with elemental lithium is a common method for the preparation of lithiosilanes and the subsequent synthesis of functionalised oligosilanes, especially of enantiomerically pure compounds. A series of alkyl- and arylsubstituted di- and trisilanes has been investigated with respect to their reactivity against elemental lithium. Thereby, depending on the substituents, silicon–silicon bond cleavage of the central Si–Si unit and/or silicon–carbon bond cleavage to arenes are observed. Quantum chemical studies provide a deeper insight into the ongoing processes. The reactive centre can be estimated by both, bond elongation after electron transfer and frontier orbital interactions (π-bonding and σ-antibonding part). Aromatic substituents at the silicon atoms proved to be necessary for the processing of any cleavage reaction in the studied systems by stabilising the radical anion after electron transfer at the corresponding di- or trisilane. Yet, selective cleavage reactions do not depend on the number of arenes.