For recent decades, non-fullerene acceptors (NFAs) are undergoing rapid development and emerging as a hot area in the field of organic solar cells. Among the high performance nonfullerene acceptors, aromatic diimide based electron acceptors remain to be the highly promising systems. This review discusses the important progress of perylene diimide (PDI)-based polymers as nonfullerene acceptors (NFAs) in all polymer solar cells (all-PSCs) since 2014. The relationship between structure and property, matching aspects between donors and acceptors and device fabrications are unveiled from a synthetic chemist perspective.