Polymer morphology has proven to be extremely important in determining the optoelectronic properties in polymer-based devices. The understanding and manipulation of polymer morphology has been the focus of electronic and optoelectronic polymer-device research. In this article, recent advances in the understanding and controlling of polymer morphology are reviewed with respect to the solvent selection and various annealing processes. We also review the mixed-solvent effects on the dynamics of film evolution in selected polymer-blend systems, which facilitate the formation of optimal percolation paths and therefore provide a simple approach to improve photovoltaic performance. Recently, the occurrence of vertical phase separation has been found in some polymer:fullerene bulk heterojunctions.1–3 The origin and applications of this inhomogeneous distribution of the polymer donor and fullerene acceptor are addressed. The current status and device physics of the inverted structure solar cells is also reviewed, including the advantage of utilizing the spontaneous vertical phase separation, which provides a promising alternative to the conventional structure for obtaining higher device performance.