We report here the synthesis and characterization of four dinuclear cyanide-bridged Fe-III-Cu-II complexes, based on a tetra- or a pentadentate bispidine ligand (L-1 or L-2, respectively; bispidines are 3,7-diazabiyclo[3.3.1]nonane derivatives) coordinated to the Cu-II center, and a tridentate bipyridineamide (bpca) coordinated to the low-spin Fe-III site, with cyanide, groups completing the two coordination spheres, one of them bridging between the two metal ions. The four structurally characterized complexes [{Fe(bpca)(CN)(3)}{Cu(L-1 center dot H2O)}]BF4, [{Fe(bpca)(CN)(3)}{Cu(L-2)}][Fe(bpca)(CN)(3)]center dot 5H(2)O, [{Fe(bpca)(CN)(3)}{Cu(L-2 center dot MeOH)}]PF6 center dot MeOH center dot H2O, and [{Fe(bpca)(CN)(3)}{Cu(L-2)}]PF6 center dot 2H(2)O belong to different structural isomers. The most important differences are structurally and electronically. enforced (direction of the pseudo-Jahn-Teller mode) strong or weak interactions of the copper(II) center with the cyanide bridge. The related strength of the magnetic coupling of the two centers is analyzed with a combination of experimental magnetic, electron paramagnetic resonance (EPR), electronic spectroscopic data together with a ligand-field theory- and density functional theory (DFT)-based analysis.