A ferrocene-initiated radical reaction of benzoquinone with amines has been successfully developed for the direct access to diaminobenzoquinone imines in high yields, in which the commercially available and cheap ferrocene was employed as a radical initiator and TBHP was used as an oxidant. Moreover, this reaction could be achieved with low loading of ferrocene (0.5 mol％). This protocol is highly efficient with good substrate tolerance and provides a new approach for the construction of benzoquinone imines with potential pharmaceutical interest.