The unprecedented ternary Te-Fe-Cu chain polymers [{Et4N}(TeFe3(CO)(9)Cu}](infinity) and [{TeFe3(CO) Cu-9(2)}(mu-4,4'-dipyridyl)(1.5)](infinity) were prepared from the self-assembly of [Et4N](2)[TeFe3(CO)(9)] with [Cu (MeCN)(4)][BF4] in THF or in the presence of 4,4'-dipyridyl in THF. These two chain polymers, which can also be constructed from the precursor complex TeFe3(CO)(9)Cu-2(MeCN)(2), show semiconducting behaviors with low band gaps of similar to 0.59 and similar to 0.41 eV, respectively. In addition, their conductivity and the effect of the bridging ligand are further elucidated by theoretical calculations.