The synthesis of poly(styrene-dimethylsiloxane) black and graft copolymers is described. Commercially available difunctional poly(dimethylsiloxane) (PDMS) containing either vinylsilyl or hydrosilyl terminal species was reacted with the corresponding hydrosilyl or vinylsilyl attachable initiators containing the benzyl chloride species. The attachment of the initiators to PDMS was achieved by hydrosilation in the presence of a platinum(0) catalyst. The terminal benzyl chloride groups were then used as initiators for atom transfer radical polymerization (ATRP) to produce block copolymers. Using this technique, triblock copolymers consisting of a PDMS centre block and polystyrene terminal blocks were synthesized. A similar process was also used to produce graft copolymers of polystyrene from a PDMS backbone.