Reactions between the complexes M3(dpa)4Cl2 (M = Co, Ni; dpa = 2,2′‐dipyridylamine), which contain linear trimetallic fragments, and (Bu4N)3[M′(CN)6] (M′ = Fe, Co) result in the formation of CN‐bridged coordination polymers. The analysis of the products obtained suggests that they have a two‐dimensional structure, in which ditopic [M3(dpa)4]2+ linkers bridge 4‐connected [M′(CN)6]3– nodes into an extended layer. The synthesis of {[Co3(dpa)4]1.97[Fe(CN)6]}Cl0.8 (1) is accompanied by an electron transfer from the tricobalt to the hexacyanoferrate units, which results in the formation of [Co3(dpa)4]3+ and [Fe(CN)6]4– fragments. In {[Ni3(dpa)4]1.74[Fe(CN)6]}Cl0.45 (3), a partial charge transfer between the trinickel and the hexacyanoferrate units leads to the temperature‐dependent FeIII/FeII mixed valence, and lower temperatures favor the thermodynamic FeIII ground state. {[Co3(dpa)4]2.06[Co(CN)6]}Cl1.1 (2) exhibits spin‐glass behavior with a spin‐freezing point of approximately 4.8 K, which is due to the magnetic superexchange between the paramagnetic [Co3(dpa)4]2+ (S = 1/2) units through the diamagnetic [Co(CN)6]3– linkers.