The reaction between the palladium(0) complex [Pd(dba) 2] [dba = dibenzylidenacetone) with TCNQ proceeds via an electron-transfer process leading to a solid having the empirical formula [Pd(TCNQ) 2(CH 3CN) x] ( x<1). The same reaction performed in the presence of a variety of ligands leads to compounds whose nature is dependent on the geometrical and electronic properties of the ligands. [Pd(dba) 2] reacts with TCNQ in the presence of 2,2′-bipyridine (bipy) affording, depending on the experimental conditions, two charge-transfer (CT) solids of general formula [Pd(bipy) 2 (TCNQ) 2], one of which exhibits spectral features of conducting TCNQ complexes. When the reaction is performed in the presence of the more steric demanding ligand, 2,9-chelating ligand, 2,9-dimethylphenanthroline (dmphen), the palladium complex [Pd(dmphen)(π-TCNQ)] is obtained. A complex with a similar stoichiometry and spectroscopic properties is obtained by reacting [Pd(dba) 2] with TCNQ in the presence of PPh 3, while by using the bis-chelating 1,2-bis(diphenylphosphino)ethane (dppe) ligand the CT salt [Pd(dppe) 2][TCQM] 2 is obtained. The CT complex [Pd(terpy)( η 1-TCNQ][TCNQ] is the product of the reaction of [Pd(dba) 2] and TCNQ in the presence of the ter-chelating 2,2′,6′,2″-terpyridine ligand (terpy). All compounds have been characterized by UV-Vis/ near-IR and IR spectroscopic techniques. X-ray photoelectron (XP) and Auger electron (XAE) spectroscopy have been employed to determine the formal charge on the palladium metal.