A versatile technique for the synthesis of multiblock copolymers of polydimethylsiloxane (PDMS) and poly(bisphenol A carbonate) (PC) is described. Specific reaction of the phenol end groups of alpha,omega -bis(bisphenol A)-terminated PDMS with the activated end groups of alpha,omega -bis(ortho-nitrophenylcarbonate)-endcapped PC yields PC-PDMS multiblock copolymers and ortho-nitrophenol. The morphology and influence of crystallization of the polycarbonate blocks is studied using solution-cast films. When THF is used as casting solvent instead of chloroform, the crystallinity of the PC blocks increases resulting in smaller domain spacings as measured by Small Angle X-ray Scattering (SAXS) and the solution-cast film has a lower strain to failure as measured by tensile testing.