The unusual synthesis of the dimeric dithiolene complex [(PPh 3 )Pd(ethylene-1,2-dithiolate)] 2 (1), containing the simplest dithiolene ligand, has been achieved through the reaction between tetrathiafulvalene (TTF) and Pd(PPh 3 ) 4 . The complex shows a folded structure in the solid state, according to single crystal X-ray analysis performed on crystals grown from two different system solvents and conditions, with a central [Pd 2 S 2 ] ring folded about the S···S hinge by 67.9°. The optimized geometry at the DFT level is in excellent agreement with the experimental structure. Moreover, TD-DFT calculations allowed the assignment of the low energy band arising at 576nm to the HOMO→LUMO transition, between frontier orbitals having mixed metal and dithiolene character.