Novel cationic Rh(I) imino-pyridine complexes were evaluated as catalyst precursors in the hydroaminomethylation of 1-octene in conjunction with both primary (aniline and benzylamine) and secondary amines (piperidine). These complexes were found to be highly efficient catalysts in mediating a one-pot hydroaminomethylation reaction. High chemoselectivities towards the target secondary and tertiary amines were obtained depending on the reaction components. Graphic