An integrated electrolysis system was built to synthesize polyaluminum chloride with ultra high-basicity and even pure Al-13. The system converts AlCl3 solution from aluminum electrode foil industry waste to Al-13 chloride directly with reasonable cost, typically $1.09 per kilogram as Al-2(OH)(5)Cl center dot 2H(2)O at 25 degrees C. Electrolyte temperature and current density were investigated to optimize the process. Ferron assay and Al-27 NMR results indicated that the purity of Al-13 is over 99% in product solutions. Ion chromatogram analysis confirmed that Cl- ions accounted for about 96.5% in all counteranions. Our integrated system is the first instance to obtain pure Al-13 polycations directly. Similar high purity products are only available after tedious purification. This effective and economic synthesis procedure has potential for mass production of Al-13 for water treatment and catalyst as well as cosmetic industries.