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Nonfullerene all-small-molecule organic solar cells (NF all-SMSCs) are an important classification in the organic solar cell system. However, the application and research of NF all-SMSCs are limited due to the easy aggregation of small molecules to form large-phase domains. Perylene bisimides (PBIs) have been widely used as nonfullerene acceptors. Simply changing the link position of the PBI dimer can control the accumulation of molecules to regulate the size of the phase domain. Herein, the bay-linked, ortho-linked, and hydrazine-linked P