Photodissociation of 2,2-diphenylhexamethyltrisilane (dphmts) has been investigated in the range from 262 to 275nm in a supersonic molecular beam. From the excitation spectrum, the S 1 origin band was determined as 36419cm −1 . We have observed the parent ion, Ph2Si(SiMe3)2+ and its various daughter ions of Ph2SiSiMe3+,Ph2SiMe+,PhSiSiMe3+,PhSiSiMe2+,PhSiMe2+,PhSi+, and SiMe3+. Occurrences of consecutive bond scissions and rearrangements with excess energy accumulated by additional photon absorption after the two-photon ionization of dphmts molecule could explain the formation of the various ionic products.