We herein report the efficient synthesis of peptide-benzazepine conjugates from Lys-based peptides and acroleins via Rh(III)-catalyzed double C-H activation. This reaction features mild reaction conditions, broad scope, high atom and step economies, and excellent chemo- and site selectivity. The synthetic utility of this strategy is further demonstrated by scale-up experiments and product derivatizations, including diverse late-stage ligations based on the aldehyde moiety. The preliminary biological activity studies show that peptide-benzazepine conjugates have good antifungal activities toward crop and forest pathogenic fungi.