The morphological and structural features of the conjugated polymer films play an important role in the charge transport and the final performance of organic optoelectronics devices [such as organic thin-film transistor (OTFT) and organic photovoltaic cell (OPV), etc.] in terms of crystallinity, packing of polymer chains and connection between crystal domains. This review will discuss how the conjugated polymer solidify into, for instance, thin-film structures, and how to control the molecular arrangement of such functional polymer architectures by controlling the polymer chain rigidity, polymer solution aggregation, suitable processing procedures, etc. These basic elements in intrinsic properties and processing strategy described here would be helpful to understand the correlation between morphology and charge transport properties and guide the preparation of efficient functional conjugated polymer films correspondingly.