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A combined computational and experimental approach allowed us to develop overall the most selective catalyst for the direct hydrogenation of N‐methyl, N‐alkyl and N‐aryl imines described to date. Iridium catalysts with a cyclometallated cyclic imide group provide selectivity of up to 99 % enantiomeric excess. Computational studies show that the selectivity results from the combined effect of H‐bonding of the imide C=O with the substrate iminium ion and a stabilizing π–π interaction with the cyclometallated ligand. The cyclometallated ligand thus exhibits a unique mode of action, serving as a template for the H‐bond directed approach of the substrate which results in enhanced selectivity. The catalyst (2) has been synthesized and isolated as a crystalline air‐stable solid. X‐ray analysis of 2 confirmed the structure of the catalyst and the correct position of the imide C=O groups to engage in an H‐bond with the substrate. 19F NMR real‐time monitoring showed the hydrogenation of N‐methyl imines catalyzed by 2 is very fast, with a TOF of approx. 3500 h−1. [ABSTRACT FROM AUTHOR]