Two-arm poly(ethylene oxide) fractions (PEOs) with arm lengths of 2220 g/mol were synthesized via a reaction using terephthaloyl (1,4-), isophthaloyl (1,3-) and phthaloyl (1,2-) dichorides as coupling agents. The center of each molecule thus includes a phenylene group as a configurational defect, and they are excluded to the crystal folded basal surfaces. In the lamellar crystals with the once-folded overall molecular conformation, observations of surface-enhanced Raman scattering experiments show that only the in-plane vibration modes are selectively enhanced. This implies that the arrangement of phenylene groups adopts a "stand-up" orientation on the basal surface, i.e., the pi plane of phenylene groups in the defects is perpendicular to the lamellar basal surface.