A rigid dimeric tetrathiafulvalene (TTF) derivative 1 doubly-bridged by dimethyltin (Me2Sn) linkers was synthesized and fully characterized. From X-ray crystallographic analysis, the central 1,4-distannine ring of 1 adopts almost planar geometry, although dication 1(2+), prepared by chemical oxidation with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TCNQ-F-4), adopts a butterfly geometry in the central 1,4-distannine ring due to the effects of the electronic structure of cationic TTFs.