1,3,5-Tris(4-carboxyphenyl)benzene assembles into an intricate 8-fold polycatenated assembly of (6,3) hexagonal nets formed through hydrogen bonds and π-stacking. One polymorph features 56 independent molecules in the asymmetric unit, the largest Z' reported to date. The framework is permanently porous, with a BET surface area of 1095 m(2) g(-1) and readily adsorbs N2, H2 and CO2.