Three two-arm poly(ethylene oxide) (PEO) fractions were prepared via a coupling reaction. These PEOs possess the same number average molecular weight of 2220 g mol(-1) for each arm and the coupling agents used are para-(I,4-), meta-(1,3-) and ortho-(1,2-) benzene dicarbonyl dichlorides. The configurations of these two-arm PEO molecules thus exhibit angles of 180, 120 and 60 degrees, respectively, at the coupling agent. These coupling agents may substantially affect the overall molecular conformations (OMCs) in the crystals of the two-arm PEOs. Wide angle X-ray diffraction powder patterns indicate that these fractions have the same crystal structure regardless of the coupling agents (which act as defects) used, and therefore the defects must be excluded from the lamellar crystals. Differential scanning calorimetry results show that two populations of crystals exist when the samples are crystallized at relatively low undercoolings. This is particularly evident in the cases of 1,4- and 1,3-two-arm PEOs. Corresponding small angle X-ray scattering experiments show two different long periods in these fractions. Experimental results reveal the possibility that the crystals which correspond to the thinner long period possess an extended OMC in which one layer of defects exists between two neighboring lamellae. The crystals which exhibit the thicker long period possess a once-folded OMC, with two layers of defects lying between neighboring lamellae. During heating, the extended OMC crystals with the thinner long period melt at lower temperatures than the thicker, once-folded OMC crystals. Detailed studies on the efforts of these configurational defects on the lamellar crystal morphology and crystal stability are discussed in the main body of the article.