Here　we　report　a　facile,　efficient,　and　catalyst-free　method　to　realize　C-C　cross-coupling　of　aryl　chlorides　and　inert　arenes　under　UV　light　irradiation.　The　aryl　radical　upon　homolytic　cleavage　of　C-Cl　bond　initiated　the　nucleophilic　substitution　reaction　with　inert　arenes　to　give　biaryl　products.　This　mild　reaction　mode　can　also　be　applied　to　other　synthetic　reactions,　such　as　the　construction　of　C-N　bonds　and　trifluoromethylated　compounds.