A ruthenium tetroxide (RuO4) staining method has been evaluated for segmented polyisobutylene-b-polybutylene terephthalate (PIB-b-PBT). Solution cast films and melt pressed samples have been studied. For comparison PBT has also been studied. PBT and PIB-b-PBT could be stained with RuO4 at room temperature. The observed structures on the PBT and PIB-b-PBT films were spherulitic with lamellae. In some regions in the PIB-b-PBT films large scale phase separation was observed. In the melt pressed PIB-b-PBT samples the spherulitic and lamellar structures were less well developed. The PBT segments appeared to have crystallized out in bundles and the PIB phase was present as microspheres with diameters of 3-6 nm.