An efficient and straightforward protocol for accessing a new series of functionalized 4-aminocoumarins from PIDA/I 2 -mediated decarboxylative C 4 -amination of coumarin-3-carboxylic acids via direct C sp2 À H dehydrogenative CÀ N cross-coupling with secondary amines under ambient conditions has been accomplished. The notable advantages of this protocol are the tolerance of diverse functional groups, mild reaction conditions at ambient temperature, moderate to good yields, short reaction times (in minutes), high regioselectivity, gram-scale applicability, and eco-friendliness. This is the first report of decarboxylative C sp2 À H cross-dehydrogenative CÀ N coupling of coumarin-3-carboxylic acids for synthesizing 4-aminocoumarins.