A metal–organic framework with a novel topology, poly[sesqui(μ2-4,4′-bipyridine)bis(dimethylformamide)bis(μ4-4,4′,4′′-nitrilotribenzoato)trizinc(II)], [Zn3(C21H12NO6)2(C10H8N2)1.5(C3H7NO)2]n, was obtained by the solvothermal method using 4,4′,4′′-nitrilotribenzoic acid and 4,4′-bipyridine (bipy). The structure, determined by single-crystal X-ray diffraction analysis, possesses three kinds of crystallographically independent ZnIIcations, as well as binuclear Zn2(COO)4(bipy)2paddle-wheel clusters, and can be reduced to a novel topology of a (3,3,6)-connected 3-nodal net, with the Schläfli symbol {5.62}4{52.6}4{58.87} according to the topological analysis.