We observe significantly improved morphology and charge transport property in films coated from amorphous solution aggregates and hypothesize this unconventional dependence of solid-state property on aggregate structure is due to its distinct assembly pathway summarized in Figure . Despite the semicrystalline nature of the nanofiber aggregates in DCB which is suggested to promote backbone alignment by previous literature , such aggregates assemble into twist-bent chiral mesophases before solidifying into thin films exhibiting twined morphology. The corresponding torsional polymer conformation, twisted polymer nanofibers and twinned morphology are not conducive to high charge carrier mobility. The semicrystalline aggregates in decane, on the other hand, form large scale disordered agglomerate driven by strong π-π interaction which cannot be disentangled nor aligned by the flow field during meniscus-guided coating leading to poor charge carrier mobility. In contrast, the amorphous, loosely associated aggregate structure in CN allows the polymer to crystallize into π-stacks during meniscus-guided coating; the crystallization process is guided by the concentration gradient and/or directional fluid flow in the evaporation regime, leading to formation of highly crystalline and aligned thin films. Such morphology further leads to desired charge transport properties.