Capacitive radio frequency (RF) discharge of c-C4F8 (octafluorocyclobutane) has been studied with synchrotron vacuum ultraviolet (SVUV) photoionization mass spectrometry (PIMS) at 4 Torr and 33.33 kHz. Various free radicals and reactive intermediates have been identified through measurement of photoionization mass spectra and photoionization efficiency (PIE) spectra. CF2=CF2 is main product in the plasma, indicating that the dissociation of c-C4F8 into CF2=CF2 is one of prominent reactions in the present experimental conditions. The observation of large species including C5F8, C5F10 and C6F10 is presented in our work. Besides, the dependences of the signals of neutral species in the discharge of c-C4F8 on RF power are presented in this paper.