Twelve ions have been observed in the dissociative photoionization studies of Mo(CO)(6) using a synchrotron radiation source in the photon energy range of 8-40 eV. The photoionization efficiency (PIE) curves of these ions from the dissociative ionization of Mo(CO)(6) have been measured for the first time. Appearance potentials (AP) of all the ions have been determined from their PIE curves and these AP values, in turn, bring about a series of bond dissociation energy (BDE) data for the intermediate ions produced by photoionization/fragmentation.