A new class of amphiphilic polymers carrying two pendant docosyl (C22) chains, located at periodic intervals that are separated by PEG chains of varying lengths, was synthesized via a simple melt-transesterification polymerization, using dimethyl, 2,5-didocosyloxyterephthalate as one of the monomers. DSC, variable temperature FT-IR, and WAXS studies demonstrated that immiscibility between the pendant docosyl units and the backbone PEG segments drives their self-segregation; this results in the crystallization of the pendant docosyl segments and the generation of a lamellar morphology with the alkyl segments and the PEG chains occupying alternate layers. Based on the study of model criss-cross amphiphiles that resemble the polymer repeat unit, it is postulated that the chains reconfigure such that both the docosyl chains fold to one side of the terephthalate unit while the PEG segments form a loop on the other side; these chains then organize in a bilayer to form the lamellar structure. The simplicity of the synthesis and the rather unique properties of these polymers suggests that such a design could be translated to develop other interesting functional materials that could exploit the immiscibility-driven microphase separation for the generation of sub-10 nm domains; these could have potential applications, such as in membranes, solid polymer electrolyte formulations, and so forth. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1554-1563