An integrated electrolysis system was built to synthesize polyaluminum chloride with ultra high-basicity and even pure Al13. The system converts AlCl3 solution from aluminum electrode foil industry waste to Al13 chloride directly with reasonable cost, typically $1.09 per kilogram as Al2(OH)5Cl·2H2O at 25 °C. Electrolyte temperature and current density were investigated to optimize the process. Ferron assay and 27Al NMR results indicated that the purity of Al13 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 Al13 polycations directly. Similar high purity products are only available after tedious purification. This effective and economic synthesis procedure has potential for mass production of Al13 for water treatment and catalyst as well as cosmetic industries.