The hypophosphorous acid was achieved with the electrodialysis, which comprises a Ti-PbO2 anode, a stainless steel cathode and an aqueous solution of sodium hypophosphite. The process of producing hypophosphorous acid was studied. Some factors, such as anodic voltage, product concentration and current efficiency were conducted. The results showed that, six-compartment electrodialytic cell could be used to improve the hypophosphorous acid content and purity. The Ti-PbO2 electrode was optimal anode material to cut down the cost of production. The process was simple, low cost and high efficient, and it was a cleaner production without waste residue and waste water.