The invention provides a method for preparing a rhodium complex catalyst from reaction waste solution of an olefin carbonylation rhodium catalyst, which is characterized by comprising the following steps: processing rhodium-containing reaction waste solution for preparing the olefin carbonylation catalyst with mixed solution of nitric acid and peroxide; reacting obtained aqueous solution with triphenylphosphine, hydrochloric acid and carbon monoxide to obtain carbonylbis(triphenylphosphine)rhodium chloride precipitation; and processing separated precipitation to convert into the rhodium (triphenylphosphine)carbonylacetylacetonate or carbonyltris(triphenylphosphine)rhodium hydride catalyst. The method has the characteristics of high recovery efficiency, simple and convenient process, mild conditions and the like.