Organic solar cells (OSCs) offer lightweight, flexibility, semi-transparency, and low manufacturing costs all in one PV technology. [1] Over the past few years, the power conversion efficiency (PCE) of OSCs has increased significantly, recently exceeding 19%, bringing this technology closer to wide-scale commercial applications. [2] The improvement in PCE is driven by the continuous development of novel materials, particularly novel non-fullerene acceptors (NFAs). [3] Commonly, highly efficient OSC devices are prepared by blending donor and acceptor materials in solution, creating a so-called bulk-heterojunction (BHJ) photoactive layer upon deposition by, for instance, spin-coating, blading, or ink-jetting. [4] The BHJ exhibits a large donor/acceptor interface area, which ensures efficient exciton quenching and charge separation as well as an interpenetrating donor-acceptor (D-A) 3D network facilitating charge carrier percolation. [5] Large D-A domain sizes of 20-50 nm are often observed in high-efficiency NFA-based BHJ cells, [6] consistent with the reported long exciton diffusion length of NFAs. [7] However, obtaining the optimal nanoscale morphology of the BHJ photoactive layer consisting of interpenetrating bicontinuous D-A networks is challenging since it is very sensitive to material properties and processing conditions. [8] Nonoptimal D-A morphologies limit charge separation and transport and thus the device performance. [9] Alternatively, bilayer structures devices are prepared by sequential deposition of the individual donor and acceptor materials. [10] In fact, layer-by-layer (LbL) coated OSCs have recently gained attention due to improved charge transport and extraction, reduced dependence of their performance on the D/A ratio and solvent used in the processing step, and often better thermal stability. [10,11] The OSC solutions and the LbL processing conditions are selected such that a pseudo-bilayer configuration is obtained, where in the center of the photoactive layer an intermixed D/A layer is created, sandwiched between the neat D and A layers. [11c,11f] Using this approach, Sun et al. achieved an impressive performance of LbL-coated OSCs based on the high-efficiency PM6:Y6 system with a PCE of %16.4%, even higher than obtained for BHJ devices (15.4%). [11a] The versatility