This paper introduces a new and effective method for preparation of PACl-electrolysis process. A series of PACl with high content of Al13 polymer was successfully prepared by electrolysis process. The amount of Al13 polymer formed in electrolysis process was found to be highly influenced by current density (di), the distance between the electrodes, electrolysis time and the stirring rate of the electrolyte. For the AlT (total aluminum concentration) of 2.0 M PACl obtained by electrolysis process, the optimal di and distance between the electrodes were 1.1 Adm(-2) and 10 mm respectively. The optimum circulating rate was 5.5 l h(-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 Al13 polymer. At the optimum condition, Al13 polymer accounted for above 70% of AlT (PACl of AlT=2.0 M and B=2.0), which was much higher than that of PACl prepared by other method.