The invention discloses a method for separating and purifying rhodium in an impurity-containing rhodium solution. The method comprises the following process steps: S1, adjusting the acidity of the rhodium solution to 6-8 mol/L, and adding a prepared DETA solution to obtain filtrate I; S2, adding aqua regia into organic rhodium salt precipitate, heating and dissolving, adding hydrochloric acid to adjust the acidity of the solution to be 6mol/L and the rhodium concentration to be 50-80g/L, heating and boiling the solution, adding ammonium chloride to generate ammonium rhodate chloride precipitate, and quickly filtering to obtain filtrate II; and adding zinc powder into the filtrate to replace rhodium ions in the rhodium solution; S3, removing trace metal impurity ions through hydrogen type cationic resin; S4, adding hydrazine hydrate for reduction to prepare rhodium black; S5, mixing replacement slag, drying, and soaking with 1: 1 hydrochloric acid to remove zinc and other metal impurities; and S6, after filtering, dissolving filter residues with aqua regia, and returning the leachate to a purification process. The method has the characteristics of high direct recovery rate, simple operation process and high purity, and qualified rhodium powder with the purity of more than 99.95% can be obtained after the rhodium black is subjected to hydrogen reduction.