The simultaneous use of nonequilibrium reaction processing and complex macromolecular architecture is an exciting way to achieve nanostructures that are not easily accessible via standard static block polymer self-assembly. Previous work has shown that the polymerization of styrene in the presence of a poly­(styrene)-block-poly­(butadiene) (PS-PBD) diblock copolymer induces a nanostructural transition from a lamellar (LAM) to a hexagonally packed cylinder (HEX) morphology. The transition was found to be driven by in situ PS grafting from the PBD block, which transforms the PS-PBD coil–coil diblock copolymer to a poly­(styrene)-block-poly­(butadiene)-graft-poly­(styrene) (PS-b-PBD-g-PS) coil–comb block polymer. In situ small-angle X-ray scattering and oscillatory shear dynamic mechanical spectroscopy measurements show that the order–order transition is not a simple epitaxial transition seen in prototypical block polymers, but undergoes a complex phase path in which the starting LAM phase at room temperature before polymerization initially disorders at elevated temperatures, evolves from a disordered phase to what is presumed to be a hexagonally perforated lamellae phase during the polymerization, and then transitions to a HEX phase on cooling to room temperature. The high-temperature phase persists for extended periods of time during the polymerization process, which allows for both the trapping and the characterization of the structure at room temperature. By utilizing nonequilibrium reactive processing to convert linear block copolymers to comb–coil type polymers, the creation of polymers with complex molecular topologies can be synthetically simplified while simultaneously allowing for the development of new processing modalities.