The invention relates to self-assembly systems formed by diphenol compounds and 2-formylbenzeneboronic acid and an application of the self-assembly systems as a fluorescence probe. According to the invention, two diphenol compounds respectively form the self-assembly systems with the 2-formylbenzeneboronic acid, the self-assembly systems can be taken as the fluorescence probe, the self-assembly systems are formed by adding the diphenol compounds and 2-formylbenzeneboronic acid in a phosphoric acid buffer, quantitative determination is carried out on free radical hypochloric acid and peroxynitrite, the probe has the advantages that the self fluorescence is weak, the fluorescence is obviously enhanced after effecting with a to-be-measured object, and compared with other detection free radical fluorescence quenching-type probes, the fluorescence probe has the characteristics of higher signal to noise ratio, rapidity, sensitivity, simpleness, and high efficiency.