摘要： D?A conjugated polymers have played critical roles in recently reported nonfullerene acceptors-based polymer solar cells (NF-PSCs) with high performance. Although the molecular design of the D?A polymers is getting more mature, there are still some fundamental unknowns to be unveiled. Here, three new D?A polymers with varied conjugated length for the D-units in their backbones, namely, PDB-1, PDB-2, and PDB-3, were designed, synthesized, and characterized. It was demonstrated that a longer D-unit leads to stronger interchain interaction and higher hole mobility for pristine polymer films. While blending with IT-4F to fabricate photoactive layers in PSCs, it was found that the domain purity, aggregation size, and π?π stacking effect of the polymers can be greatly affected by the D-unit size. Compared to polymers with shorter D-units, for the polymer with the largest D-units (PDB-3), hole and electron transport channels can be much more easily formed in the blend films. Interestingly, the highest efficiency was obtained in the PSCs based on a PDB-2:IT-4F blend, in which PDB-2 shows similar D-unit size to the polymers with state-of-the-art high photovoltaic performance. The correlations between the molecular structure and photovoltaic property of PDB-x polymers demonstrate that the modulation of building block size is an important method for designing high-performance D?A conjugated polymers for PSCs.