In this work, we performed a systematic comparison of different duration of solvent vapor annealing (SVA) treatment upon state-of-the-art PM6:SY1 blend film, which is to say for the first time, the insufficient, appropriate, and over-treatment’s effect on the active layer is investigated. The power conversion efficiency (PCE) of corresponding organic solar cell (OSC) devices is up to 17.57% for the optimized system, surpassing the two counterparts. The properly tuned phase separation and formed interpenetrating network plays an important role in achieving high efficiency, which is also well-discussed by the morphological characterizations and understanding of device physics. Specifically, these improvements result in enhanced charge generation, transport, and collection. This work is of importance due to correlating post-treatment delicacy, thin-film morphology, and device performance in a decent way.