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The single bulk‐heterojunction active layer based on non‐fullerene acceptors (NFAs) has dominated the power conversional efficiencies above 18% in state‐of‐the‐art organic solar cells (OSCs). However, a deep understanding of the relationship between charge carrier process and film microstructure remains unclear for emerging NFA OSCs. Herein, with the superstar PM6:Y6 blend as a model, the charge generation process in active layers is successfully manipulated by designing three different film microstructures, and they are correlated with the final photovoltaic performance in OSC devices. The amount of intermediate intra‐moiety excited states from the nanoscale Y6 aggregates can be effectively enhanced by controlling the phase separation domains and film crystallinity in the bicontinuous PM6:Y6 networks. This robustly improves the hole transfer, and thus promotes charge generation. As a result, the optimal films show superior device performance, that is, the high efficiencies of 16.53% and 17.98% for PM6:Y6‐ and D18:Y6‐based single junction OSCs, respectively. The results presented here give a rational guide for optimizing the charge carrier process through controlling morphological microstructures toward high‐performance NFA OSCs.

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Solid-state microstructures of conjugated polymers are essential for charge transport in electronic devices. However, precisely modulating aggregation pathways of conjugated polymers in a controlled fashion is challenging. Herein, we report a sequential aggregation approach via selectively modulating side chain aggregation in solution state and backbone aggregation during film formation to increase H-aggregates and consequently enhance hole mobility of printed diketopyrrolopyrrole-based polymer (PDPP-TVT) film. The sequential aggregation is realized by introducing 1-bromonaphthalene additive into chloroform solvent. The structural evolution and assembly pathways of PDPP-TVT in initial solution and during printing were revealed using small-angle neutron scattering, cryogenic transmission electron microscopy, and time-resolved optical diagnostics. The results show that the poor interactions between PDPP-TVT side chains and BrN triggers side chain aggregation to form large H-aggregate nuclei in initial solution. The additive further selectively forces backbone aggregation on H-aggregate nuclei during printing with dynamics increasing from ca. 3 to >1000 s. Such prolonged growth window and selective growth of H-aggregates produce large fibers in printed film and therefore 3-fold increase in hole mobility. This work not only provides a promising route toward high-mobility printed conjugated polymer films but also reveals the important relationship between assembly pathways and film microstructure.