Trifluoromethylsulfonyl fluoride (CF₃SO₂F) is a novel environmentally friendly insulation gas that has attracted widespread attention due to its excellent insulation strength and environmental friendliness. This paper identifies the emission spectra of CF₃SO₂F under different discharge modes and analyzes the emission spectral characteristics of radiative particles from the discharge perspective. During corona discharge, CF₂ emitted a band spectrum of 200 to 400nm due to the dissociation of CF₃SO₂F. The associated steady-state decomposition products include CF₄, C₂F₄, C₂F₆, C₃F₈, SO₂F₂, etc. As the energy provided by the electric field increases, overlapping line and band spectra occur in surface discharge emission spectra. A few elemental particles undergo ionization. In spark discharge, where the energy provided by the electric field is highest, line spectra dominate the emission spectra. Multiple levels of ionization of elemental particles occur. With the increase in energy supplied by the electric field, the ratio of photons in the visible and infrared spectral regions exhibits a “red-shift” phenomenon. The research results indicate that the emission spectra formed by gaseous molecules or elemental particles during partial discharge correlate with steady-state decomposition products. The appearance of characteristic spectra confirms the existence of free radical reactions, while the different ratios of photons reflect the amount of energy provided by the electric field. This study can provide references for the basic physical and chemical properties research of CF₃SO₂F.