A dinuclear zinc complex containing both a sigma-dimerized 7,7,8,8-tetracyanoquinodimethane (TCNQ) ligand ([TCNQ-TCNQ](2-)) and TCNQ(-) was synthesized for the first time. This is the first instance of a single molecular complex with a bridging [TCNQ-TCNQ](2-) ligand Each zinc center is coordinated with two 2,2'-bipyrimidines and one TCNQ(-), and the remaining coordination site is occupied by a [TCNQ-TCNQ](2-) ligand, which bridges the two zinc centers. The complex facilitates g-stacking of TCNQ(-) ligands when crystallized, which gives rise to a near-IR charge-transfer transition and strong antiferromagnetic coupling.