The present invention relates to a method of separating and purifying phenol in a simple and economical manner, by employing a step of adding high pressure carbon dioxide to the aqueous phenol solution to form a solid clathrate of phenol. According to the method of separating phenol of the present invention, phenol can be separated from the highly concentrated phenol solution without employing solvent or post-treatment step, finally to give 100 mole % of a solid phenol and 0.6 mole % of an aqueous phenol solution by employing only one step. Moreover, since the method is carried out at the temperature of below room temperature without excess energy consumption, the separation of phenol can be made in a simple and economical manner.