A series of tetraalkylthio substituted tetrathiafulvalenes (TTC n-TTF) was prepared. The syntheses, molecular and crystal structures, and physical properties of TTC n-TTF reveal marked differences from those of BEDT-TTF. The conformational change of TTC 1-TTF molecule on the formation of charge transfer complexes and the mode of the S… S contacts are described in connection with those of BEDT-TTF compounds.