The efficient palladium-catalyzed synthesis of esters from readily available arenes has been developed. These C-H bond esterifications were achieved relying on the regioselective thianthrenation to generate the aryl-TT salts, which were treated as reactive electrophilic substrates to couple with phenol formate and N-hydroxysuccinimide (NHS) formate giving access to phenol esters and NHS esters, respectively, in the absence of carbon monoxide. A wide range of functional esters could be prepared with high efficiency under this redox-neutral palladium-catalytic condition. Late-stage functionalization and investigations of synthetic applications demonstrated the potential application of the established platform and these products.