Two three-dimensional (3D) coordination polymers, viz. [Ni(INAIP)(Him)(H2O)]·H2O (1) and [Fe(INAIP)(H2O)2]·H2O (2), were synthesized by reaction of 5-(isonicotinamido)isophthalic acid (H2INAIP), NiSO4·6H2O/FeSO4·7H2O, and N-donor ligands, namely 1H-imidazole or 4,4′-bipyridine, under hydrothermal conditions. Single-crystal X-ray diffraction analysis indicated that [Ni(INAIP)(Him)(H2O)]·H2O has a two-dimensional (2D) layer network structure with (6, 3) topology, while 2 shows a 3D fourfold interpenetrating framework with (103-b) topology. The thermal stability and magnetic and adsorption behavior in solid state of the complexes were investigated in detail. Moreover, the photocatalytic degradation of methylene blue (MB) over complex 1 was studied.