The first paramagnetic 4d transition-metal complex with a redox-active tetrathiafulvalene ligand has been synthesized. The preparation, X-ray structure, electrochemistry, and electron paramagnetic resonance measurements of [Ru(salen)(PPh3)(TTF-CH=CH-Py)](BF4) [1(BF4)] are reported. The crystal structure reveals that the paramagnetic Ru(III) (s = 1/2) center is in a tetragonally elongated octahedral geometry and the TTF-CH=CH-Py ligand is coordinated to the axial position of the Ru(III) ion through the nitrogen atom of the pyridine group. Thus, 1(BF4) is an attractive precursor to study future pi-4d interactions in dual-property conducting and magnetic materials.