A two-dimensional and bifunctional pillar-layered metal–organic framework (MOF)—with the molecular formula [Zn(cba)(bpdb)]·DMF (2DTMU-1), H2cba = 4,40 -methylenedibenzoic acid, bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene—was obtained via the reaction of zinc(II) nitrate with H2cba as the carboxylate linker and bpdb as the N-donor pillar. 2DTMU-1 is based on a binuclear paddlewheel Zn(II) unit complexed by four bridging bidentate (dicarboxylate) V-shaped ligands, which combine to from H2cba; this tetragonal array, which is connected by bpdb with a bridging azine group, presents a pore size of 18 × 12 Å2 .