The reaction of Cd(ClO₄)₂ with the bulky anthracene-9,10-dicarboxylic acid (H₂L) in the presence of 2,6-dimethylpyridine afforded a three-dimensional (3-D) metal-organic framework (MOF) {[Cd₂(L)₂(H₂O)₄](C₂H₅OH)_0.75(H₂O)_1.25}_∞(1) (L = anthracene-9,10-dicarboxylate) which exhibited an unusual (3,4)-connected (6.8²)₂(6.8⁵) topology and also strong solid-state luminescent emission with a stable lifetime originating from an intraligand π→π* transition.