Free radical bicyclization/chloroalkylarylation of 1,7-dienes/enynes with polychloromethane was finished to access diverse polychloromethyl-revised fused heterocycles. Meanwhile, polychloromethane could selectively undergo HAT or XAT to give relevant polychloromethyl radicals, which only carried out subsequent 6-endo bicyclization processes. In addition, various scaled-up operations and radical inhibition and radical clock experiments were studied to verify the application and reaction pathway.