This paper introduces a new and effective method for preparation of PACl-electrolysis process. A series of PACl with high content of Al 1 3 polymer was successfully prepared by electrolysis process. The amount of Al 1 3 polymer formed in electrolysis process was found to be highly influenced by current density (d i ), the distance between the electrodes, electrolysis time and the stirring rate of the electrolyte. For the Al T (total aluminum concentration) of 2.0 M PACl obtained by electrolysis process, the optimal d i and distance between the electrodes were 1.1 Adm - 2 and 10 mm respectively. The optimum circulating rate was 5.5 lh - 1 . Because of the inhomogeneous pH between the surface of cathode and the bulk solution, the electrolysis process has the advantage to form more Al(OH) 4 - as precursor of Al 1 3 polymer. At the optimum condition, Al 1 3 polymer accounted for above 70% of Al T (PACl of Al T =2.0 M and B=2.0), which was much higher than that of PACl prepared by other method.