Graphene Oxides (GOs) have been frequently employed as fillers in polymer-based applications. While GO is known to nucleate polymer crystallization in GO-polymer composites reinforcing the mechanical properties of semicrystalline polymers, its counter effect on how polymer crystallization can alter the microstructure of GO has rarely been systematically studied yet. In this work, we study the GO nematic liquid crystal (LC) phase during polymer crystallization focusing on their hierarchical structures by employing in situ small/wide-angle X-ray scattering/diffraction (SAXS/WAXD) techniques. We found that GO LC and polymer crystals co-exist in the GO/polymer complex, where the overall liquid crystallinity is influenced by polymer crystallization. While polymer crystallizes in bulk or at the interface depending on the cooling rate, the interfacial crystallization of poly(ethylene glycol) (PEG) on GO improves both GO alignment and orientation of PEG crystal. This work provides an opportunity to develop a hierarchical structure of GO-based crystalline polymer nanocomposites, whose directionality can be controlled by polymer crystallization under proper cooling rates.