Fragment ion-photon coincidence (FIPCO) spectra by 120 eV electron impact on trifluoromethane (CHF₃) have been observed, in which optical emission in the 200-600 nm region has been detected. The CF₃⁺, CHF₂⁺, CF₂⁺ and CF⁺ ions were observed in the FIPCO spectra. The kinetic energy distributions of these ions were estimated on the basis of the Monte Carlo simulation of their observed band shapes. Considering the total kinetic energy release in the dissociation processes producing CF₃⁺ and CHF₂⁺, we have concluded that the production of CF₃⁺ and CHF₂⁺ follows the D-B and D-C emissions of the parent ion, respectively. The CF₂⁺ and CF⁺ ions were correlated with the Balmer emission from the excited hydrogen atom. These dissociation processes producing CF₂⁺ and CF⁺ take place after the excitation to singly charged superexcited states of CHF₃.