The photoionization spectrum of BrO was measured over the wavelength range lambda = 106-122 nm using a discharge-flow photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. BrO was generated by the reaction of O(3P) atoms with molecular bromine. A value of 10.46 +/- 0.02 eV was obtained for the adiabatic ionization energy of BrO from photoion thresholds, corresponding to the BrO+ (X 3SIGMA-)<--BrO(X 2PI3/2) transition. Spectra for both the (BrO)-Br-79 and (BrO)-Br-81 isotopes were very similar and the resultant photoion thresholds were identical, within experimental uncertainty. The structure observed in the spectra is discussed in terms of available states for BrO+, which have been calculated using MC-SCF methods.