Controlling polymorphism in ordered molecular solids through manipulation of processing method has been rarely addressed despite its significance in creating assembled molecular materials with desired functions. We here report a hyperbranched liquid-crystalline polymer that showed variable lamellar smectic phases, depending on the processing methods by regulation of the kinetics involved assembly process to control the molecular packing arrangement in different lamellar arrays. The processing-dependent polymorphism enabled multicolored light emission of the liquid-crystalline polymer including cyan, green, and yellow light, showing variant degree of bathochromic shift with respect to the blue fluorescence in highly dilute solution. With a good correlation between the processing methods, hierarchically assembled structures, and light emission properties of the hyperbranched liquid crystalline polymer, it would have broad implications in pathway-dependent supramolecular self-assembly and provide a guidance for the development of adaptive functional materials in different situations.