Mesomorphic phase structures in blends of sulfonic acid-terminated poly(ethylene glycol) (sPEG) and tertiary amino-terminated poly (2-ethylhexyl methacrylate) (aP2EHMA) were investigated by small angle X-ray scattering technique. SAXS results suggest the blends form lamellar morphology regardless of the blend composition between 30 and 70 wt% in sPEG. The blend containing 50 wt% of sPEG forms the highest ordered lamellar morphology and variation of the composition causes distortion of the ordered morphology. Due to the dissociating and reconstructing natures of the non-covalent bond between the sPEG and aP2EHMA, the lamellar morphology is maintained with the variation of the composition.