The chemiluminescence spectrum in the optical cavity of discharge-driven hydrogen fluoride (HF) chemical laser is measured. The result reveals that the spectra of the helium and fluorine (F) atoms are the major components. Moreover, the green chemiluminescence in the downstream of the optical axis is mostly composed of the 60P20 spectral line of the HF molecule. The analysis shows that, except for the cold pumping reaction, the recombination of the F atoms and the hot pumping reaction also occur in the optical cavity. Due to the hot pumping reaction and the optical cavity temperature in a specific range, the 60P20 line becomes the strongest HF molecule in the downstream region of the optical axis. After the hot pumping reaction, the green chemiluminescence always appears in the downstream region of the optical axis when the optical cavity temperature varies in a greater range.