Three new heterobimetallic coordination polymers (CPs), {[Ni(4-pytpy)2][Ag(CH3CN)(NO3)](NO3)2(H2O)2}n1 (4-pytpy = 4′-(4-pyridyl)- 2,2′:6′,2′′-terpyridine), {[Ni(4-pytpy)2][Ag2(4,4′-bipy)](NO3)4(DMSO)4}n2 (4,4′-bipy = 4,4′-bipyridine), and {[Ni(4-pytpy)2][Cu3(SCN)5](CH3CN)(DMF)(H2O)0.5}n3, were synthesized from metalloligand [Ni(4-pytpy)2]2+ with transition metals and different bridging ligands. All three compounds were characterized by elemental analysis, Fourier-transform infrared spectroscopy, thermal analysis and single-crystal X-ray diffraction analysis. Both CPs 1 and 2 display one-dimensional (1D) chain structures, which are further extended to 3D supramolecular structures through hydrogen bonds. CP-3 features a 2D network, which is constructed from 1D double chain cluster structure {[Cu3(SCN)5]2−}n linked by metalloligands [Ni(4-pytpy)2]2+ and exhibits an unusual (3,3,4)-connected 3-nodal topology. Thermal analysis indicates that the dehydrated structures of 1 and 3 can be stable up to 310 °C. The solid-state luminescence properties of compounds 1–3 were also investigated.