Reactions of CuCl2, K2[Ni(CN)4]/K3[Co(CN)6], and 5-amino-1H-tetrazole led to cyanide-bridged mixed-valence Cu(II/I) complexes, [Cu(H2O)3Cu3(CN)5] (1) and [Cu(H2O)4][Cu4(CN)6] (2).The uncommon semi-closed {Cu2(CN)3} dimmers in 1 are bridged by μ3-C,C,N cyanide ligands to afford rare 1D centipedal-like chain motifs, which are further bridged by μ2-C,N and metalloligand “CN–Cu(4)–CN” to finish sophisticated zeolite-like 3-D structure. Topologically, 1 is the first example of uninodal 7-connected sev-like cyanide-bridged network. Compound 2 consists of two-dimensional honeycomb-related anionic layers [Cu4(CN)6]2−, within which the [Cu(H2O)4]2+ cations are intercalated into alternate interlamellar space. Compound 1 shows antiferromagnetic couple arising from pure ground-state configuration of Cu(II) mediated by diamagnetic bridges –CN–CuI–CN−. The inclusion compound 2 shows blue photoluminescence originated from Cu(I) center to the unoccupied π* orbital of the cyanide ligand (MLCT) charge transfer.