All-polymer solar cells (All-PSCs) are of great interest as a renewable and economically viable energy technology, which has shown potential advantages in practical photovoltaic applications due to the highly tunable optical, electronic, and mechanical properties. A quantitative understanding of the domain composition variations and orientational ordering of all-polymeric films affected by solvent additives had been unattainable until now. This study demonstrates how the use of trace amount solvent additive can indeed manipulate domain purity and molecular orientational ordering as revealed by polarized soft X-ray scattering (P-SoXS). Additionally, the BDDT/PNDI all-polymeric blend exhibits enhanced average domain purity with the use of a trace amount of solvent additive and thus improved charge mobility, device fill factor and power conversion efficiency. A high power conversion efficiency of ∼7.1% was obtained in the All-PSC mainly contributed by this morphology control strategy. Manipulation of domain purity and orientation ordering, both of which are impacted by the aggregation kinetics, may be a key to further boost the efficiency of new fullerene-free solar cells and all-anisotropic materials-based devices.