Block copolymers consisting exclusively of a siliconoxygen backbone are synthesized by sequential anionic ring-opening polymerization of different cyclic siloxane monomers. After formation of a poly(dimethylsiloxane) (PDMS) block by butyllithium-initiated polymerization of D3, a functional second block is generated by subsequent addition of tetramethyl tetravinyl cyclotetrasiloxane (D4(V)), resulting in diblock copolymers comprised a simple PDMS block and a functional poly(methylvinylsiloxane) (PMVS) block. Polymers of varying block length ratios were obtained and characterized. The vinyl groups of the second block can be easily modified with a variety of side chains using hydrosilylation chemistry to attach compounds with Si-H bond. Conversion of the hydrosilylation used for polymer modification was investigated.