Experimental and theoretical studies of intramolecular assistance by carbonyl groups and heteroatoms in the electron transfer driven cleavage of the carbon-tin bond of tetraalkylstannanes has been carried out. Carbonyl groups and heteroatoms (oxygen and nitrogen) in an appropriate position of tetraalkylstannane facilitate the electron transfer and selective cleavage of the carbon-tin bond. Although the coordination of the carbonyl groups and heteroatoms to tin was not detected in the neutral molecules, molecular orbital calculations indicate that the coordination of such groups to tin in the cation radical intermediate stabilizes the system and weakens the carbon-tin bond. These results offer striking examples of the intramolecular assistance of electron transfer driven reactions.