A pronounced enhancement of the power conversion efficiency (PCE) by 38% is achieved in one-step doctor-blade printing organic solar cells (OSCs) via a simple solvent vapor annealing (SVA) step. The organic blend composed of a donor polymer, a nonfullerene acceptor, and an interfacial layer (IL) molecular component is found to phase-separate vertically when exposed to a solvent vapor-saturated atmosphere. Remarkably, the spontaneous formation of a fine, self-organized IL between the bulk heterojunction (BHJ) layer and the indium tin oxide (ITO) electrode facilitated by SVA yields solar cells with a significantly higher PCE (11.14%) than in control devices (8.05%) without SVA and in devices (10.06%) made with the more complex two-step doctor-blade printing method. The stratified nature of the ITO/IL/BHJ/cathode is corroborated by a range of complementary characterization techniques including surface energy, cross-sectional scanning electron microscopy, grazing incidence wide angle X-ray scattering, and X-ray photoelectron spectroscopy. This study demonstrates that a spontaneously formed IL with SVA treatment combines simplicity and precision with high device performance, thus making it attractive for large-area manufacturing of next-generation OSCs.