We present a unique interpretation of X-ray absorption spectroscopy (XAS) spectra at Cu:K, W:L-3, and Mo:K edges of structurally related magnetic Cu-II-[M-V(CN)(8)](3-) compounds. The approach results in description of the structure of novel three-dimensional (3-D) Cu-3(II)(pyz)-[M-V(CN)(8)](2)center dot xH(2)O, M = W (1), Mo, (2) polymers. Assemblies 1 and 2 represent hybrid inorganic-organic compounds built of {Cu-II[W-V(CN)(8)](-)}(n) double-layers linked by cyanido-bridged {Cu-II-(mu-pyz)(2+)}(n) chains. These Cu-II-M-V systems reveal long-range magnetic ordering with T-c of 43 and 37 K for 1 and 2, respectively. The presence of the 3-D coordination networks and 8 cyanido-bridges at M-V centers leads to the highest Curie temperatures and widest hysteresis loops among Cu-II-[M-V(CN)(8)](3-) systems.