The organic donor tetrathiafulvalene (TTF, 1) and its derivatives are synthesized from tetrathianaphthalene (TTN, 2) in a one pot reaction. The reaction takes advantage of an isomerization of lithiated TTN into lithiated TTF and subsequent substitution with novel disulfide electrophiles yielding substituted T donors. The isomerization approach eliminates the need for a chemical coupling reaction of oxones or thiones (a yield limiting procedure), and simple byproducts eliminate the need for tedious purification. The novel methodology allows for a high yield preparation of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF, 3a, 80%) and bis(propylenedithio)tetrathiafulvalene (BPDT-TTF, 3b), previously unavailable directly from TTF. A high yield of bis(phenylenedithio)tetrathiafulvalene (BPhDT-TTF, 3c, unavailable from dimercaptoisotrithione “DMIT”) is also achieved using the synthetic scheme. The method is general, and can be used to prepare a variety of novel organic donors based on TTF. Synthetic procedures along with all relevant characterization are presented.