The very dense (d = 4.359 g cm−3) three dimensional (3D) hybrid heterometallic framework Bi3O2Cu(OH)(pdc)2 (pdc3−:3,5-pyrazoledicarboxylate), 1, features a 2D inorganic subnetwork representing an unprecedented topological type, and is an effective catalyst for the diastereoselective synthesis of E-α,β-unsaturated ketones.