Numerous previous reports on the sequential deposition (SD) technique have demonstrated that this approach can achieve a p‐i‐n active layer architecture with an ideal vertical composition gradient, which is one of the critical factors that can influence the physical processes that determine the photovoltaic performance of organic solar cells. Herein, a commonly used photovoltaic system comprised of PM6 as a donor and Y6 as an acceptor is investigated with respect to sequential blade‐processing deposition to comprehensively explore the morphology characteristics as a function of baseplate temperature. A systematic study of the temperature‐dependent blend morphology elucidates the SD‐processed configuration merits and device physics behind temperature‐controlled degree of vertical composition gradient, and constructs the temperature‐microstructure‐property relationship for the corresponding photovoltaic parameters. The result shows, as the temperature increases, the morphology of the active layer has undergone a distinct evolution from the pseudo‐bulk heterojunction to a pseudo‐planar heterojunction and then to a pseudo‐planar bilayer, leading to a non‐monotonic correlation between baseplate temperature and device performance. This investigation not only reveals the importance of precisely controlling baseplate temperature for gaining vertical morphology control, but also provides a path toward rational optimization of device performance in the lab‐to‐fab transition.