The tetrathiafulvalene-scaffold (TTF) reacts selectively in allylation, acylation, arylation, halogenation, and thiolation reactions via magnesium or zinc derivatives that are obtained by a direct metalation with Mg- and Zn-TMP-bases (TMP = 2,2,6,6-tetramethylpiperidyl). This stepwise functionalization provides access to a range of new mono-, di-, tri-, and tetra-functionalized TTF-derivatives and allows for fine-tuning of their energy levels.