The novel bimetallic FeIIAgI thermal-induced spin crossover coordination polymer {FeII(3,5-dimethylpyridine)2[AgI2(CN)3][AgI(CN)2]}n was synthesized by one-pot reactions between 3,5-dimethylpyridine and K[AgI(CN)2] in the presence of FeII salt (FeSO4·(NH4)2SO4·6H2O). Magnetic studies demonstrate the occurrence of a spin transition. The crystal structure has been studied at 293 K and 80 K. The compound is made up of unprecedented three-dimensional networks topology of FeII ions bridged by binuclear [AgI2(CN)3]− and mononuclear [AgI(CN)2]− units; [AgI2(CN)3]− anion is very rare. In this complex, the presence of the AgI ions plays a significant role in increasing the dimensionality and cooperatively due to the triangular argentophilic interactions.