The power conversion efficiencies (PCEs) of spin-coated organic solar cells (OSCs) have increased rapidly in recent years. However, spin-coating shows poor reproducibility for large-scale production. Slot-die coating, a lab-scale version of roll-to-roll fabrication, has been considered as the most suitable technique for the production of future large-area commercial devices. For this, the highly efficient slot-die-fabricated devices are required to approach the performance of spin-cast OSCs. We present here, a nonfullerene OSC device utilizing the PBDB-T/i-IEICO-4F blend, fabricated by slot-die coating without post-treatment in the ambient conditions. The device showed an impressive PCE of 12.5%, which is one of the highest reported performance for slot-die-coated OSC devices. Compared to the spin-coated and blade-coated films with optimized thermal annealing time, the films fabricated by slot-die coating (without any treatment) exhibit not only the highest degree of crystallinity and face-on orientation but also the smallest domain size and the purest phase toward enhanced and balanced carrier mobilities. An enhanced excited-state charge generation has been attributed to transient charge kinetics using ultrafast spectroscopic signatures. The optimized slot-die-coated devices exhibit excellent tolerance for the increased thickness of the photoactive layer, attributing to favorable molecular packing. We used slot-die coating as a simple fabrication technique, which is capable of yielding highly efficient OSCs.