An efficient metal free protocol has been developed for the synthesis of benzylic esters via a cross dehydrogenative coupling (CDC) involving alkylbenzene(s) as a self- or as a cross-coupling partner(s) via the intermediacy of Ar–COOH and the benzylic carbocation obtained from the other half of the alkylbenzene; both symmetrical as well as unsymmetrical esters can be prepared using Bu4NI and TBHP.