In an electrolytic cell having cation exchange membrane as diaphragm to partition said cell into cathode and anode chambers, electrolysis of an electrolyte aqueous solution is conducted while generating gas from anode by keeping the inner pressure in cathode chamber higher than that in anode chamber. Some disadvantages caused in the case of electrolyzing an aqueous alkali metal halide solution to form alkali metal hydroxide in cathode chamber are overcome by adjusting the anolyte at pH