The selective mono-N-methylation of anilines using methanol as an alkylating reagent was achieved with high efficiency under the catalysis of well-defined rhenium complexes bearing tridentate diphosphinoamino ligands and in the presence of a base. The reaction proceeds well for a large scope of anilines (32 examples) with low loadings of both the catalyst (down to 0.5 mol%) and the base (Cs2CO3, down to 5 mol%). The mechanism of the reaction was investigated by DFT (PBEO-D3) calculations. (C) 2018 Elsevier Inc. All rights reserved.