A cost-effective route for the synthesis of hydroxylamine chloride (NH2OH center dot HCl) was proposed by combining ammoximation and oxime hydrolysis reactions (A-O-H route). This route is limited by low equilibrium conversion of oxime hydrolysis, which is a reversible reaction that produces ketone and NH2OH center dot HCl. A pervaporation membrane reactor (PVMR) was recommended in this route for improving butanoxime hydrolysis conversion by in situ removal of byproduct butanone. Using a PDMS membrane, the effects of feed composition, temperature, and reactant concentration on the PVMR performance were investigated. An enhancement of conversion from about 20% to 84% was achieved. When using a high reactant concentration, NH2OH center dot HCl can be crystallized in the PVMR. The longtime experiment demonstrated that the membrane was stable in acidic and ionic environments in the reaction mixture.