Two novel metal-organic frameworks (MOFs) based on transition metals, namely [Ni(sbdc)(4,4′-bbibp)(H2O)2]n (1) and [Co(sbdc)(4,4′-bbibp)]n (2) (H2sbdc = 4,4′-stilbenedicarboxylic, 4,4′-bbibp = 4,4′-bis(benzoimidazo-1-ly)biphenyl), have been designed and successfully synthesized under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 5-fold classical Ia interpenetrated dia framework with 4-connected (66) sqc6 topology and complex 2 displays a 7-fold classical Ia interpenetrated dia network. Further, the photocatalytic properties of complexes 1–2 have been investigated. Significantly, the complexes 1–2 are good photo-catalysts for the degradation of organic dyes (MB/MV/RhB).