Single-phased La_0.6Sr_0.4Co_1-yFe_yO_3-δ (y = 0.2, 0.5, 0.8) nanorods exhibiting the rhombohedral perovskite-type phase were synthesized by a pore-wetting technique. We studied their chemical composition, crystal and electronic structures, morphology and hyperfine properties as a function of the Co/Fe content of the samples. Our results demonstrate that Co cations exhibit a slightly lower oxidation state than Fe ones, resulting in a higher oxygen non-stoichiometry δ for Co-rich samples. In addition, the values of δ determined in this work for nanostructured samples are much higher than those reported in the literature for bulk materials. This can be attributed to the high number of defects in nanomaterials and is probably one important factor in the high electrochemical performance for the oxygen reduction reaction of nanostructured La_0.6Sr_0.4Co_1-yFe_yO_3-δ IT-SOFC cathodes, which have been reported in a previous work.