For the first time, by using H₃PO₃/I₂ system, various benzyl chlorides, bromides and iodides were dehalogenated successfully. In the presence of H₃PO₃, benzyl halides underwent electrophilic substitution reactions with electron-rich arenes, leading to a broad range of diarylmethanes in good yields. These transformations feature green, cheap reducing reagents and metal-free conditions. A possible mechanism was proposed.