Treatment of [Fe2(eta-C5H5)2(mu-CO)2{mu-Ph2PN(Et)PPh2}] with 7,7,8,8-tetracyano-p-quinodimethane, TCNQ, affords, on crystallization from acetonitrile, a charge-transfer salt, [Fe2(eta-C5H5)2(mu-CO)2{mu-Ph2PN(Et)PPh2}]2(TCNQ)3.2MeCN, with a novel 2:3 stoichiometry; the cations and anions in this species are distributed in segregated stacks, the TCNQ anions packing as trimers along the stack with an intratrimer separation of 3.24(1) angstrom and an intertrimer separation of 3.39(1) angstrom.