A new nickel-macrocyclic complex [Ni(L)]·CH2Cl2 (1, L = C24H22N4O3) was synthesized based on a bent oxadiazole bridging ligand terminated by tetradentate N2O2 Schiff-base units. Two novel Ni−Ag mixed-metal, mixed-valence, and cluster-containing coordination polymers, namely, [Ag2Ni(L)](ClO4)2.5 (2) and [Ag2Ni(L)](BF4)2.5 (3), generated from 1 and AgX (X = ClO4−, BF4−) were synthesized. During the reactions, unexpected metal-exchange and metal valence-change were observed. These two Ni−Ag coordination polymers are isostructural. They all feature a two-dimensional double-layered concavo-convex structure which is composed of a dual-bowl unit and mixed-valent NiII2NiIII2 cluster node. Compounds 1−3 were fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the luminescent properties of 1−3 were investigated primarily.