Photoionization of W(CO)(6) in the photon energy range of 8-40 eV produced a variety of intermediate ions of the form (WCm(CO)(n))(x)+). Photoionization efficiency (PIE) curves of these ions have been measured for the first time by using a time-of-flight mass spectrometer (TOFMS) with vaccum ultraviolet (VUV) photons from a synchrotron radiation source. Appearance potentials (AP) of all the observed ions have been determined from their PIE curves. Based on these AP values, we obtained a series of bond dissociation energy (BDE) data for the intermediate ions produced by the dissociative photoionization. (C) 1997 American Institute of Physics.