AbstractThe first high yield preparation of non π‐stabilized bis(lithio‐methyl)silanes was performed by the reductive cleavage of C–S bonds with electron transfer reagents. Bis[(phenylthio)‐methyl]silanes synthesized by the reaction of dichlorosilanes with [(phenylthio)methyl]lithium were transformed to the corresponding bis(lithiomethyl)silanes7by reaction with lithium naphthalenide (LiC10H8) or lithiump,p′‐di‐tert‐butyl‐biphenylide (LiDBB) as an electron transfer reagent and were characterized by their reaction with Bu3SnCl. The C–S bonds of bis[(phenylthio)methyl]silanes can be cleaved selectively making possible the introduction of two different groups. – The silicon atom plays a central role in the reactivity of the presented structural types. The bis(lithiomethyl)silanes are used as new building blocks for the preparation of organosilanes, Si–H‐functionalized organosilanes, and 1,3‐disilacyclobutanes contain