A practical Cu-catalyzed picolinamide-directed o-amination of anilines showing excellent mono-substitution selectivity and high functional group tolerance has been developedWe thank the Spanish Government (MINECO, CTQ2012-35790) and the Madrid regional government (AVANCAT, S2009/PPQ-1634) for financial support. N.R. thanks the MICINN for a Ramon y Cajal contract and the Marie Curie Foundation (CIG: CHAAS-304085