Following photodissociation of 2-chloro-1,1-difluoroethene CF2CHCl) at 193 nm, vibration-rotationally resolved emission spectra of HCl(vless than or equal to3) and HF(vless than or equal to4) in spectral regions 2000-2900 and 3050-4410 cm-1, respectively, are detected with a step-scan time-resolved Fourier-transform spectrometer. All vibrational levels of HCl and HF show Boltzmann-type rotational distributions. HCl has an average rotational energy of 23+/-4 kJ mol(-1) and a vibrational energy of 25+/-5 kJ mol(-1), whereas HF has an average rotational energy of 20+/-4 kJ mol(-1) and a vibrational energy of 48+/-6 kJ mol(-1). The observed internal energy distribution indicates that HCl is produced via the three-center (alpha,alpha), but HF via the four-center (alpha,beta) elimination. A modified separate statistical ensemble model predicts an internal energy distribution of HCl slightly greater than experimental observation. A modified impulse model taking into account geometries and displacement vectors of transition states during bond breaking predicts satisfactorily the rotational excitation of HF produced from four-center elimination. Ratios of rate coefficients (0.87:0.13) predicted for three-center or four-center elimination channels based on Rice-Ramsperger-Kassel-Marcus theory are consistent with a branching ratio of 0.88:0.12 determined based on observed populations of HCl and HF, respectively. We also compare these experimental and theoretical results with those of photolysis of vinyl halides (CH2CHX, X=F, Cl, or Br) at 193 nm.