The invention discloses an on-line measuring system and method for the concentration of NO3 free radicals in the atmosphere based on broadband cavity-enhanced absorption spectroscopy. The on-line measuring system at least comprises a light source controller, a light source, a first convex lens, a second convex lens, a pair of high-reflectivity lenses, a detection cavity, an optical fiber, a spectrometer and a zero-point generator. According to the invention, the pair of high-reflectivity lenses compose a resonant cavity, a LED is used as the light source, and the spectrometer is used as a detector; dynamic zero points are employed for elimination of the influence of other absorbed components on the measurement of NO3 free radicals, so on-line accurate measurement of the NO3 free radicals in the atmosphere is realized. The on-line measuring system and method provided by the invention have the characteristics of low detection limit, high sensitivity, high temporal-spatial resolution, high stability and low cost.