In this work, we present the combination of two characteristics that are beneficial for solid oxide fuel cell (SOFC) cathodic performance in one material. We developed and evaluated for the first time nanostructured layered perovskites of formulae LnBaCo₂O_6-d with Ln = Sm and Gd (SBCO and GBCO, respectively) as SOFC cathodes, finding promising electrochemical properties in the intermediate temperature range. We obtained those nanostructures by using porous templates to confine the chemical reagents in regions of 200-800 nm. The performance of nanostructured SBCO and GBCO cathodes was analyzed by electrochemical impedance spectroscopy technique under different operating conditions using Gd₂O₃-doped CeO₂ as electrolyte. We found that SBCO cathodes displayed lower area-specific resistance than GBCO ones, because bulk diffusion of oxide ions is enhanced in the former. We also found that cathodes synthesized using smaller template pores exhibited better performance.