The mixed solvent approach has been demonstrated as a promising method to modify nanomorphology in polymer solar cells. This work aims to understand the unique role of the additive in the mixture solvent and how the optimized nanoscale phase separation develops laterally and vertically during the non-equilibrium spin-coating process. We found the donor/acceptor components in the active layer can phase separate into an optimum morphology with the additive. Supported by AFM, TEM and XPS results, we proposed a model and identified relevant parameters for the additive such as solubility and vapor pressures. Other additives are discovered to show the ability to improve polymer solar cell performance as well.