The invention discloses a high purity rhodium recovery purification method, relates to precious metal recovery purification field, and especially relates to a method for separation and purification of rhodium from other precious metals and base metals in a rhodium-containing waste leachate. According to the method, tetramethylammonium chloride is used as a precipitant, the rhodium solution concentration is controlled to 30-80 g / L, firstly, a small amount of precipitant is added for reaction to remove platinum, iron and other high valence impurities, excessive precipitant is added into the obtained filtrate for boiling and reflux at 110-120 DEG C for 24 h-48 h to obtain a rhodium salt precipitate. High purity rhodium hydroxide is obtained by full washing, dissolving, passing through resin, and potassium hydroxide precipitation carried out on the rhodium salt precipitate. The high purity rhodium recovery purification method is strong in process applicability, simple in operation, low in cost, high in product purity, and free of emission, and may not cause environmental pollution.