Hydrogen-bonding interaction between the two components of the poly( ethylene oxide) (PEO)/oligoester (OER) blends and the PEO/crosslinked unsaturated polyester resin (PER) blends was found to be an important driving force to the miscibility of these polymer blends. Its strength is approximately as strong as the self-association of hydroxyl groups in either the pure GER or the pure PER. The crystallization kinetics and morphology of PEO in PEO/PER blends was remarkably affected by crosslinking. It was found that the overall crystallization rate of PEG in PEO/PER blends is larger than that in PEO/OER blends at the crystallization temperature investigated, which was considered to be the result of nucleation controlling mechanism. With decreasing PEG content, the regular shape of PEO spherulites turns irregular in PEO/OER blends, whereas in PEO/PER blends, the birefrigent spherulites turns into dendritic structures. Raising the crystallization temperature favors the formation of dendritic textures in PEO/PER blends.