With plenty of popular and effective ternary organic solar cells (OSCs) construction strategies proposed and applied, its power conversion efficiencies (PCEs) have come to a new level of over 19% in single-junction devices. However, previous studies are heavily based in chloroform (CF) leaving behind substantial knowledge deficiencies in understanding the influence of solvent choice when introducing a third component. Herein, we present a case where a newly designed asymmetric small molecular acceptor using fluoro-methoxylated end-group modification strategy, named BTP-BO-3FO with enlarged bandgap, brings different morphological evolution and performance improvement effect on host system PM6:BTP-eC9, processed by CF and ortho-xylene (o-XY). With detailed analyses supported by a series of experiments, the best PCE of 19.24% for green solvent-processed OSCs is found to be a fruit of finely tuned crystalline ordering and general aggregation motif, which furthermore nourishes a favorable charge generation and recombination behavior. Likewise, over 19% PCE can be achieved by replacing spin-coating with blade coating for active layer deposition. This work focuses on understanding the commonly met yet frequently ignored issues when building ternary blends to demonstrate cutting-edge device performance, hence, will be instructive to other ternary OSC works in the future.