The process of electrochemical amination of chlorobenzene using hydroxylamine and the Ti(IV)/Ti(III) mediator system is studied in aqueous solutions of 6–16 M sulfuric acid containing acetic acid or acetonitrile. The substitution products in these media are isomeric chloroanilines and chlorophenylenediamines, with the exception of 5-chloro-1,3-isomer, phenylenediamines, and aniline. The overall current efficiency of amino compounds corresponding under the experimental conditions to the efficiency by hydroxylamine can reach 71%. Para- and ortho-chloroanilines are obtained in 6 M sulfuric acid and 11.1 M acetic acid with the weight fraction and current efficiency of 97 and 51%, respectively.