The invention provides a method for complexing and separating chromium and vanadium in chromium and vanadium contained acid liquid. The method comprises the following steps: (1) returned amine organicmatters are added in chromium and vanadium acid liquid under the conditions of a certain temperature and pH value; and few fresh amine organic matters are added; vanadium in the acid liquid and the amine organic matters generate a complexing reaction to generate precipitates; and chromium dose not generate a complexing effect with the amine organic matters; (2) obtained solid-liquid mixtures arefiltered to obtain chromium-contained acid liquid after vanadium separation and complexing precipitates of vanadium; (3) the complexing precipitates of vanadium are structurally converted in alkali substances to realize dissociation of vanadium and the amine organic matters; and (4) the solid-liquid mixtures in above steps are filtered to obtain inorganic precipitates of vanadium and dissociated amine organic matters; and under alkaline condition, the dissociated amine organic matters can be circularly used for complexing and separation process of chromium and vanadium under acid condition. The vanadium and chromium complexing and separating method is high in vanadium and chromium separation rate, prevents mutual inclusion of vanadium and chromium, and meanwhile, is simple in flow, mild incondition, wide in operation range and easy to apply to industrial production.