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In organic photovoltaic cells, the solution-aggregation effect (SAE) is long considered a critical factor in achieving high power-conversion efficiencies for polymer donor (PD)/non-fullerene acceptor (NFA) blend systems. However, the underlying mechanism has yet to be fully understood. Herein, based on an extensive study of blends consisting of the representative 2D-benzodithiophene-based PDs and acceptor-donor-acceptor-type NFAs, it is demonstrated that SAE shows a strong correlation with the aggregation kinetics during solidification, and the aggregation competition between PD and NFA determines the phase separation of blend film and thus the photovoltaic performance. PDs with strong SAEs enable earlier aggregation evolutions than NFAs, resulting in well-known polymer-templated fibrillar network structures and superior PCEs. With the weakening of PDs' aggregation effects, NFAs, showing stronger tendencies to aggregate, tend to form oversized domains, leading to significantly reduced external quantum efficiencies and fill factors. These trends reveal the importance of matching SAE between PD and NFA. The aggregation abilities of various materials are further evaluated and the aggregation ability/photovoltaic parameter diagrams of 64 PD/NFA combinations are provided. This work proposes a guiding criteria and facile approach to match efficient PD/NFA systems. A systematic study of the representative organic photovoltaic systems shows that the aggregation competition between polymer donor (PD) and non-fullerene acceptor (NFA) is a decisive factor in the phase separation of blend film and thus the photovoltaic performance. Based on 64 PD/NFA combinations, the aggregation ability/photovoltaic parameter heatmaps are plotted, providing a new matching rule for developing high-efficiency PD/NFA systems. image, Funding Agencies|National Natural Science Foundation of China; Jiangsu Provincial Departments of Science and Technology [BK20220010, BE2022023]; Natural Science Foundation of Jiangsu Province [BK20221317]; Science and Technology Development Fund, Macao SAR [FDCT-0082/2021/A2]; UM's research fund [MYRG2022-00241-IAPME, MYRG-CRG2022-00009-FHS]; [52273295]; [52303236]; [61935017]; [51903239]; [62288102]; [62175268]