A purification method for separating and purifying an organic solvent from a liquid mixture of an organic solvent and water, the organic solvent having a boiling point of more than 100° C. at 1 atm, includes the steps of: passing the liquid mixture through a first ion exchange device; supplying the liquid mixture discharged from the first ion exchange device to a pervaporation device to selectively separate water component; supplying the organic solvent recovered from the concentration side of the pervaporation device to an evaporator to obtain a purified organic solvent; and passing, through the second ion exchange device, a portion of liquid containing the organic solvent and flowing at a first position subsequent to the first ion exchange device. The liquid discharged from the second ion exchange device is returned to a second position which is at a preceding stage of the pervaporation device.