Two new metal–organic frameworks based on cyclic-type dodecanuclear copper units, (Me 4 N) 6 [Cu 12 (OMe) 6 (pz) 6 (BTC) 6 ]·18H 2 O 1 and (Me 4 N) 6 [Cu 12 (OH) 6 (pz) 6 (BTC) 6 ]·21H 2 O 2 (pz=pyrazolate, BTC=1,3,5-benzenetricarboxylate), have been prepared by the solvothermal reactions of copper salts, Hpz and H 3 BTC ligands. The cyclic-type Cu 12 unit in 1 and 2 is constructed by twelve Cu II ions linked together by μ 2 -OH or μ 2 -OMe and unidentate carboxylate groups at the inner- and μ-pz and bidentate carboxylate groups at the outer surface of the toroid. In 1 and 2, each Cu 12 unit is connected to 12 other units by BTC linkers, leading to 12-connected three-dimensional porous frameworks. The photocatalytic investigations indicate that compounds 1 and 2 exhibit photocatalytic activity for the degradation of RhB.