AbstractA novel and facile method for the synthesis of 3‐(2‐oxo‐2‐arylethyl)chroman‐4‐ones under metal‐free conditions is described. In the presence of nBu4NBr and K2S2O8, arylaldehydes or aliphatic aldehydes with various functional groups could react with different 2‐(allyloxy)arylaldehydes via radical process to produce chroman‐4‐one derivatives in moderate to good yields. The method features metal‐free, step‐economical manner and easily available starting materials, exhibiting its practical synthetic value in some biologically active compounds.