By ruthenium/acid dual catalysis, we present, for the first time, a transfer hydrogenative para-selective aminoalkylation of aniline derivatives with N-heteroarenes. Position-2 of the sterically less-hindered pyridine ring of the N-heteroarenes couples with various aniline derivatives at the site para to the amino group, affording a wide array of structurally modified anilines, a class of highly valuable compounds with the potential for discovery and further creation of functional molecules. The developed chemistry features operational simplicity, a readily available catalyst system, excellent functional group tolerance, and exclusive regioselectivity, which offers a significant basis to access novel aniline derivatives that are currently inaccessible or challenging to prepare with conventional approaches, and design new coupling reactions via a hydrogen transfer strategy.