An array of perfectly alternating polycarbonate-polydimethylsiloxane (PC-PDMS) multiblock copolymers possessing systematic variations in block molecular weights were successfully produced by coupling preformed PC and PDMS telechelic oligomers using hydrosilylation. Based on gel permeation chromatography results, the multiblock copolymers were essentially void of the oligomeric precursors. Despite the relatively large difference in solubility parameter between PC and PDMS, the multiblock copolymers exhibited significant partial miscibility between the two phases. As expected, the degree of partial miscibility was dependent on the molecular weight of the blocks with the extent of partial miscibility increasing with decreasing block molecular weights. Morphological characterization using small angle X-ray scattering showed that, at a given PC block molecular weight, the uniformity of the two phase morphology increased with increasing PDMS block molecular weight, which is consistent with a decrease in the extent of phase mixing with increasing PDMS block molecular weight. (C) 2013 Society of Plastics Engineers