The complicated dissociative photoionization of Si(CH3)(2)Cl-2 has been investigated with photoionization mass spectrometry (PIMS) and a synchrotron as source of vacuum ultraviolet (VUV) radiation. We determined appearance energies (AE) of the parent cation Si(CH3)(2)Cl-2(+), and various ionic fragments -Si(CH3)(2)Cl+, Si(CH3)Cl+, Si(CH3)Cl+, etc. - originating from photofragmentation. The appearance energy of Si(CH3)(2)Cl-2(+) is 10.41 eV, in agreement with measurements of the photoelectron spectrum. Relative photoexcitation spectra of individual fragment ion yields are obtained and the dissociative processes are discussed. A comparison of Si(CH3)(2)Cl-2 and Si(CH3)Cl-3 provides insight and understanding of fragmentation processes on dissociative photoionization of gaseous chlorosilanes. (C) 2004 Elsevier B.V. All rights reserved.