Object: This invention provides a method of refining an Rh-containing solution also containing at least one type of impurities of heavy metals, alkaline earth metals, and Ag.Means for solving the problems: The invention provides a method of refining an Rh-containing hydrochloric acid solution also containing Ag and at least one other impurity of heavy metals and alkaline earth metals, the method comprising the steps of: (a) adding an alkali to the solution to adjust pH of the solution to 7-12, whereby generating a neutralized precipitate containing Rh and other components; (b) filtrating and separating the neutralized precipitate; (c) adding a first hydrochloric acid for redissolving the neutralized precipitate in an amount such that the mole ratio of Cl to Rh (mole ratio Cl/Rh) of a resulting solution becomes 3-4; (d) filtering the resulting solution to remove Ag as precipitate, and (e) extracting the solution obtained by the previous step as an aqueous phase with DEHPA.