A novel dioxime, N,N bis[2 (2 iminohydroxyphenoxy)ethyl] toluenesulfonamide(BIHET), was synthesized and characterized, and a carbon paste electrode modified with BIHET was employed for electroanalysis of iron(Ⅲ) from aqueous solutions. The electrochemical redox reaction of the dioxime with the modified CPE and the electrochemical behavior of iron(Ⅲ) on the CPE were investigated.