This paper reports two new fluorine-substituted polymer donors (BO2FC8, BO2FEH), with different side-chain architectures, and a new chlorine-substituted small-molecule acceptor (m-ITIC-OR-4Cl) that are capable of simultaneous charge and energy transfer as the binary blend active layer for organic photovoltaics. We first resolved the single-crystal structure of m-ITIC-OR-4Cl and then used simultaneous grazing-incidence wide- and small-angle X-ray scattering to decipher the multi-length-scale structures—such as the shape and size of aggregated domains and molecular orientation—of the blends of BO2FEH and BO2FC8 with m-ITIC-OR-4Cl. The linear side chains of BO2FC8 facilitated its packing and, thus, induced m-ITIC-OR-4Cl to form smaller disc-shaped aggregated domains (thickness: 2.9 nm) than its aggregate domain (thickness: 5.4 nm) in the blend of the branched BO2FEH. That is, the binary blend system of linear-side-chain BO2FC8 with m-ITIC-OR-4Cl featured larger interfacial areas and more pathways for charge transfer and transport, as evidenced by their carrier mobilities. The highest power conversion efficiency (PCE) of 11.0% was that for the BO2FC8:m-ITIC-OR-4Cl device, being consistent with the predicted PCE of 11.2% using machine learning based on random forest algorism; in comparison, the PCE of the BO2FEH:m-ITIC-OR-4Cl device was 6.4%. This study has not only provided insight into the photovoltaic performances of new polymer donor/small-molecule acceptor blends but has also, for the first time, deciphered the hierarchical morphologies—from molecule orientation to nano-domain shape and size—of such blend systems, linking the morphologies to the photovoltaic performances. The use of side-chain architectures suggests an approach for tuning the morphology of the polymer/small-molecule binary blend active layer for use in organic photovoltaics.

Semitransparent organic photovoltaics (ST‐OPVs) have great potential for use in renewable energy technologies. In bulk‐heterojunction (BHJ) ST‐OPVs, a compromise is necessary between the visible light transmittance (VLT) and the power conversion efficiency (PCE). A sequential deposition (SD) strategy that involves individually depositing a polymer donor layer (D) and a small‐molecule acceptor layer (A) as the active layer is presented; where molecular diffusion occurring at the interfacial region results in a pseudo p–i–n structure. PBDB‐T‐2F(D)/Y6(A) ST‐OPVs are fabricated with different active layer thicknesses—at 115 nm, the SD (D:A/75:40 nm) and BHJ devices (D:A/1:1.2 w) provide the champion PCE of 12.91% (VLT of 14.5%) and 12.77% (VLT of 13.4%), respectively; at 85 nm, the SD (D:A/45:40 nm) and BHJ devices (D:A/1:1.2 w) provide a PCE of 12.22% (VLT of 22.2%) and 11.23% (VLT of 16.6%), respectively. This trend indicates SD devices have larger PCE and VLT values than the BHJ devices at a given active layer thickness, and the enhancements of PCE and VLT values by the SD structures against the BHJ structures become more pronounced as the active layer thickness reduced. The SD strategy provides a new approach for achieving ST‐OPVs with both high efficiency and high transparency.