The present invention uses proper extractant to extract organic solvent from aqueous solution containing organic alkali (or its salt), adds extractant and excess inorganic alkali to the raffinate phase water layer to extract organic alkali into extractant then separates with water. The two raffinates are fractional distilled separately to recover organic alkali, and at the same time, the obtainedextractant can be cyclically used. Advantages: reduce production cost, reduced environmental pollution, simple process, and easy to operate.