The group 14 chains Me3CSiMe2GeMe2SnR3 (R= Me (1a), Ph (1b)) have been synthesized, and 1b has been characterized by single-crystal X-ray analysis. Photochemical irradiation of 1a leads to the elimination of the elements of either Me2Ge or Me2Sn and cleavage of the Ge-Sn bond. Treatment of 1a with n-BuLi results in formation of [Me3CSiMe2GeMe2]-Li+ and Me3Sn (n-Bu).