A preparation method of PVA fiber comprises the following steps: preparing a spinning dope; PVAc is used as a raw material, and dissolved with addition of methanol before filtration, and then the spinning dope is obtained; spinning; the spinning dope is injected into a spinneret, and the ejected fibers are brought into a direct current electrolytic cell, and undergo a series of reactions of alcoholysis, electrolytic catalytic alcoholysis, and the levering of the alcohol; and the solution formulation in the electrolytic coagulation bath comprises alkali, alcohol and water; acid bath; through stretching, drying, washing with water, crimping with hot water and packaging, a finished polyvinyl alcohol fiber product is formed. The mirabilite is not needed in the coagulation bath, and PVA is obtained by the alcoholysis of PVAc in an electrolytic cell, and the produced PVA fibers present high purity and few impurities.