Co oxides with perovskite-related structure are particularly promising, cost-effective OER catalysts. However, the increasing Co demand by the battery industry is pushing the search for Co-free alternatives. Here we investigate the potential of the Co-free layered perovskite family RBaCuFeO5+δ (R = 4f lanthanide), where we identify the critical structural and electronic variables leading to high OER catalytical performance. The employed methodology, based in the use of advanced neutron and X-ray synchrotron techniques combined with ab initio DFT calculations allowed to reveal LaBaCuFeO5+δ as new, promising Co-free electroctalyst. Moreover, we could show that this material can be industrially produced in nanocrystalline form. We believe that the reported results and methodology may contribute to the implementation of new technologies aimed to generate energy with lower carbon emissions, and can also inspire the scientific community in their search of other Co-free materials with good OER electrocatalytical properties.