A method of direct contact membrane distillation (DCMD) with a self-made hollow polyvinylidene fluoride membrane was applied to prepare high concentration polyaluminum chloride (PACl) with high A1b content based on chemical synthesis. The permeate flux and A1 species distribution were investigated. The experimental results showed that the permeate flux decreased from 14 to 6 kg/(m2 x hr) at the end of the DCMD process, which can be mainly attributed to the formation of NaCl deposits on the membrane surface. The Alb content decreased slightly, only from 86.3% to 84.4%, when the DCMD experiment finished, correspondingly the A1c content increased slightly from 7.2% to 8.5%, and the A1a content remained at 7% during the whole DCMD process. A PACl with A1b content of 84% at total aluminum concentration 2.2 mol/L was successfully prepared by the chemical synthesis-DCMD method.