The invention discloses a method for judging the existence of the high-efficiency quantum well structure of the multiple quanta well LED, which is to conduct the spectral scan and measurement on the luminous surface of LED by utilizing the line-by-line scanning of the microspectrofluorimeter according to the change of the injection current, and judge the existence of the high-efficiency quantum well structure according to the evolvement of the measured microscopic luminescent spectral-line. The method provided in the invention is easy to operate without destructibility, which can not only make clear the quantum structure in the epitaxial layer of the multiple quanta well, but also promote in time the improvement of the processing technique. The method can also predict the luminous efficiency under the working current, which is propitious to application classification of the apparatus products and is significant to the updating and upgrading of products, reduction of cost and improvement of productivity effect.