Display omitted •Three nanolayered polymorphs are found in a comb-like di-alkoxylated polyester.•Flash DSC is used to study the liquid crystalline (LC) state in quenched samples.•Transitions from modification B to A and from A to LC are studied by DSC and XRD.•Crystal orientation is observed in case of ram extruded polymer fibers.•Oriented nanolayered states are also seen in case of polymer coated glass fibers. Structure formation in an alkoxylated polyester having rigid backbone and flexible side chains composed of 10 alkyl carbons per side chain is studied using X-ray diffraction, conventional DSC and flash DSC techniques. Two crystalline states-modification B and modification A are observed with their occurrence depending on the thermal treatment. Additionally, a liquid crystalline phase is also detected above the melting temperature of modification A. While modification B is the thermodynamically preferred phase at low temperatures consisting of crystalline side chains, modification A is observed on heating above 120 °C and shows a disordered packing of the side chains. Rapid cooling using Fast Differential Scanning Calorimetry (FDSC) yields a liquid crystalline state wherein a long range ordered layered morphology exists, however, the π − π stacking of the backbones is absent. The molecular orientation of backbones under the influence of shear fields as well as on a glass fiber surface is also studied. Both modifications A and B show backbone orientation along the shear fields in an extruded sample while a preferential edge-on orientation is inferred on the glass fiber surface.