Four new cyano-bridged bimetallic complexes, [{Mn-III(salen)}(2){Fe-III(qcq)(CN)(3)}(2)](n)center dot 3nCH(3)CN center dot nH(2)O (1) [salen = N,N'-ethylenebis(salicylideneiminato) dianion; qcq(-) 8-(2-quinoline-2-carboxamido)quinoline anion], [{Mn-III(salpn)}(2){Fe-III(qcq)(CN)(3)}(2)](n)center dot 4nH(2)O (2) [salpn = N,N'-1,2-propylenebis(salicylideneiminato)dianion], [{Mn-II(bipy)(CH3OH)}{Fe-III(qcq)(CN)(3)}(2)](2)center dot 2H(2)O center dot 2CH(3)OH (3) (bipy = 2,2'-bipyridine), and [{Mn-II(phen)(2)}{Fe-III(qcq)(CN)(3)}(2)]center dot CH3CN center dot 2H(2)O (4) (phen = 1,10-phenanthroline) have been synthesized and characterized both structurally and magnetically. The structures of 1 and 2 are both unique 1-D linear branch chains with additional structural units of {Mn-III(salen/salpn)}{Fe-III(qcq)(CN)(3)} dangling on the sides. In contrast, 3 and 4 are cyano-bridged bimetallic hexanuclear and trinuclear clusters, respectively. The intermolecular short contacts such as pi-pi interactions and hydrogen bonds extend 1-4 into high dimensional supermolecular networks. Magnetic investigation reveals the dominant intramolecular antiferromagnetic interactions in 1, 3, and 4, while ferromagnetic and antiferromagnetic interactions coexist in 2. Alternating current measurement at low temperature indicates the existence of slow magnetic relaxation in 1 and 2, which should be due to the single ion anisotropy of M-III.