Photoionization and dissociative photoionization of HFC-152a have been studied using synchrotron radiation and a reflectron time-of-flight mass spectrometry (RTOF-MS). The ionization energy of parent molecule (11.94±0.04eV) and appearance potentials of various fragment ions have been determined by measuring their photoionization efficiency curves. Energies, symmetry point groups and ground electronic states of neutrals and cations of parent and its fragments have been calculated using GAUSSIAN-03 program with the G3 method. According to the theoretical and experimental results, some dissociation channels and their dissociation energies of CH3CHF+2 have been analyzed.