Two zinc-phosphites modified by a rigid amine 3,5-bis(imidazole-1-yl)pyridine (BIP), [Zn2(HPO3)2(BIP)]·H2O (1) and [Zn3(HPO3)3(BIP)(H2O)]·H2O (2), were solvothermally prepared. Compound 1 possesses a zincophosphite layer decorated by BIP moieties via coordinating to intralayer Zn(ii) ions. Compound 2 features a 3D frame with a pillar-layer structure, in which the organic BIP pillars the inorganic zincophosphite layer via coordinating to interlayer Zn(ii) ions. The structural diversity from a 2D layer to a 3D frame was mainly attributable to the different bridging modes of BIP in the process of assembly. Their temperature-dependent photoluminescence properties have also been studied.