This paper reports how the morphology of a polymer–fullerene derivative blend is tuned via the different aggregate states of the polymer in solutions. Based on a copolymer with benzodiothiophene and thiophene-3-carboxylate as alternating units (PBDTCT), we explored the polymer aggregation (i.e., organo-gels) behavior as a function of steric hindrance of aromatic solvents imposed by substituents. We showed that the size of organo-gels decreased as the substituents of solvents got larger. Also, the phase separation and domain size of the subsequent spin-coated films increased monotonically with that of the organo-gels in solution. Through this knowledge, we eventually achieve controlled morphology and optimized organic solar cells (OSCs) performance. Our results present a significant step forward for understanding the self-assembly behavior of conjugated polymers, control of their morphology and optimization of OSC performance.