In this work, three unique Tb III -carboxylate frameworks with the formula {[Tb 2 (OH) 2 (H 2 O) 2 (abtc)]·2H 2 O} n ( 1 ), {[Tb 2 (abtc) 1.5 (H 2 O) 3 (DMA)]·H 2 O} n ( 2 ) and {[Tb 3 (abtc) 2.5 (H 2 O) 4 ]·H 3 O} n ( 3 ), each displaying structural variations, have been successfully synthesized by the solvothermal reactions of Tb(NO 3 ) 3 ·6H 2 O with the azo-containing ligand 3,3',5,5'-azobenzene tetracarboxylic acid (H 4 abtc) under varying conditions. Detailed single-crystal X-ray diffraction (SC-XRD) analysis manifested a remarkable diversity in these structures, demonstrating various coordination patterns of Tb III -metal nodes with the carboxylate groups of the organic linker, which contributed to the generation of intricate three-dimensional (3D) coordination networks with remarkable chemical resistance. Furthermore, frameworks 2 and 3 , characterized by porous networks containing two and three independent Tb III -metal nodes, respectively, were both demonstrated to be efficient heterogeneous catalysts toward the cyanosilylation of imines under mild conditions with excellent reusability. In addition, direct current ( Dc ) magnetic susceptibility measurements conducted on frameworks 1 , 2 , and 3 indicated that there were obvious antiferromagnetic interactions among the Tb III -metal nodes, which suggests the involvement of intricate intra - and intertrimer exchange channels, adding another fascinating dimension to their physical properties.