- The photodissociation of chlorodifluoromethane, CHF2Cl (HCFC-22), was studied by a laser pump-and-probe technique, using 193 nm excitation of the parent molecule and a time-of- flight mass spectrometer combined with (2+ 1) resonance-enhanced multiphoton ionization to detect products. Photolysis via two channels, C− Cl and C− H bond rupture, was observed, while HCl elimination was not found. The H, Cl (2P3/2) and Cl (2P1/2) yields are found to be first order in the photolysis and third order in the probe laser intensity. The H/Cl and Cl (2P1/2)/Cl (2P3/2) branching ratios are 0.19±0.06 and 0.36±0.03, respectively. The mechanism of the dissociation is discussed in view of these results.