The luminescent complexes [Cd(BIMP)2(NDC)2]n and [Zn(BIMP)2(NDC)]n (where (3-BIMP) = 3-(1H-benzoimidazol-2-yl)pyridin-2(1H)-one and NDC = 2,6-naphthalenedicarboxylic acid) have been synthesised under hydrothermal conditions and their crystal structures determined. [Cd(BIMP)2(NDC)2]n exhibited a 1D → 2D → 3D framework structure and [Zn(BIMP)2(NDC)]n has a 3D porous structure. Under the same excitation energy (λex = 389 nm), [Zn(BIMP)2(NDC)]n showed a stronger fluorescence emission than the free 3-BIMP ligand, the NDC ligand and [Cd(BIMP)2(NDC)2]n.