The addition of chiral 2,2'4-2,6-pyridinediy)bis(4-isopropyl-2-oxazoline) (iPr-Pybox) to a self-assembled Co-II-[W-V(CN)(8)] magnetic system gives two enantiomorphic cyano-bridged chains, {[CoII((S,S)-iPr-Pybox)(MeOH)](3)[W-V(CN)(8)](2)center dot 5.5MeOH center dot 0.5H(2)O}(n) (1 - SS) and {[Co-II((R,R)-iPr center dot Pybox) (MeOH)](3)[W-V(CN)(8)](2)center dot 5.5MeOH center dot 0.5H(2)O](n) (1-RR). Both compounds crystallize with a structure containing a unique crossed arrangement of one-dimensional chains that form a microporous supramolecular network with large channels (14.9 angstrom x 15.1 angstrom x 15.3 angstrom) filled with methanol. The investigated materials exhibited optical chirality, as confirmed by natural circular dichroism and UV-vis absorption spectra. 1-(SS) and 1-(RR) are paramagnets with cyano-mediated Co-II-W-V magnetic couplings that lead to a specific spin arrangement with half of the W-V ions coupled ferromagnetically with their Co-II neighbors and the other half coupled antiferromagnetically. Significant magnetic anisotropy with the easy axis along the [101] direction was confirmed by single-crystal magnetic studies and can be explained by the single-ion anisotropy of elongated octahedral Co-II sites. Below 3 K, the frequency-dependent chi(M)''(T) signal indicated slow magnetic relaxation characteristic of single-chain magnets.