Vertically self-assembled bilayers with an interfacial bottom layer and a photoactive top layer are demonstrated via a single coating step of a blend composed of an amine-containing nonconjugated polyelectrolyte (NPE) and an organic electron donor-acceptor bulk heterojunction composite. The self-assembled NPE layer reduces the work function of an indium tin oxide (ITO) cathode, which leads to efficient inverted organic solar cells without any additional interface engineering of the ITO.