The dissociative photoionization of CH2Br2 in a region ∼10–24 eV was investigated with photoionization mass spectroscopy using a synchrotron radiation source. An adiabatic ionization energy of 10.25 eV determined for CH2Br2 agrees satisfactorily with predictions of 10.26 and 10.25 eV with G2 and G3 methods, respectively. Observed major fragment ions CH2Br+, CHBr+, and CBr+ show appearance energies at 11.22, 12.59, and 15.42 eV, respectively; minor fragment ions CHBr2+, Br+, and CH2+ appear at 12.64, 15.31, and 16.80 eV, respectively. Energies for formation of observed fragment ions and their neutral counterparts upon ionization of CH2Br2 are computed with G2 and G3 methods. Dissociative photoionization channels associated with six observed fragment ions are proposed based on comparison of determined appearance energies and predicted energies. An upper limit of ΔHf,2980(CHBr+)⩽300.7±1.5 kcal mol−1 is derived experimentally; the adiabatic ionization energy of CHBr is thus derived to be ⩽9.17±0.23 eV. Literature values for ΔHf,2980(CBr+)=362.5 kcal mol−1 and ionization energy of 10.43 eV for CBr are revised to be less than 332 kcal mol−1 and 9.11 eV, respectively. Also based on a new experimental ionization energy, ΔHf,2980(CH2Br2+) is revised to be 236.4±1.5 kcal mol−1.