With alkyl carbazates as the green ester source, a novel palladium‐catalyzed oxidative free radical carbonylative transformation of the C–H bond on aromatic rings to produce esters has been developed. Good yields of the corresponding products have been obtained with wide functional group tolerance and excellent regioselectivity. A variety of alkyl carbazates are found to be suitable reactants for the ortho‐alkoxycarbonylation on the aromatic ring.