The present invention contemplates for providing a producing method which can give highly pure caustic potash in a relatively simple process, in response to the above-described demand for increased high purity in caustic potash. A method to give highly pure caustic potash containing almost no impurities of sodium, chlorine, and heavy metals, such as iron, chromium and nickel, through crystallization, by bringing an aqueous caustic potash solution having a sodium content of 200 mg/kg or less and a chlorine content of 15 mg/kg or less when calculated in terms of a weight of potassium chloride, in which a caustic potash concentration of 48% is to be a standard, into a high temperature state.