In this paper, based on Differential Optical Absorption Spectroscopy (DOAS) technique, experimental measurements of chlorine was carried out in the laboratory with a small self-built experimental system. In dealing with the standard cross-section of chlorine, we presented two different methods: triangle filtering and polynomial fitting. Experiments showed that the concentration of chlorine could be accurately retrieved by the latter one. Simulation results showed that the error of retrieval result by fifth-order polynomial fitting was smaller than by other orders and an actual retrieval example shows that the fitting spectrums were nearly coincident with the measured spectrums with a residual delta(peak to peak) below 5‰; The results measured in different sample pools displayed a high linearity of 0.996 1 by this method. The main sources of errors during the entire experiment were simply analyzed. According to the experimental result above, it is feasible to detect chlorine using DOAS technology by polynomial fitting.