In this letter a method is described to synthesize new polysiloxane architectures by photoacid catalysis. An oxasilaspirocycle is designed that is able to undergo a photoacid generator catalyzed ring-opening reaction leading to either a homopolymer or to copolymers with hydroxyl-terminated polydimethylsiloxane. These polymers feature a defined amount of double bonds in the backbone, which is controlled by the ratio of oxasilaspirocycle to the comonomer. The former was prepared by trispentafluorophenylborane-catalyzed intramolecular hydrosilylation of a dialkenyloxysilane with an appropriate structural motif. The UV-initiated polymerization was characterized via in situ IR spectroscopic studies to determine the rate of reaction.