With the demonstration of small-area, single-junction polymer solar cells (PSCs) with power conversion efficiencies (PCEs) over the 10% performance milestone, the manufacturing of high-performance large-area PSC modules is becoming the most critical issue for commercial applications. However, materials and processes that are optimized for fabricating small-area devices may not be applicable for the production of high-performance large area PSC modules. One of the challenges is to develop new conductive interfacial materials that can be easily processed with a wide range of thicknesses without significantly affecting the performance of the PSCs. Toward this goal, we report two novel naphthalene diimide-based, self-doped, n-type water/alcohol-soluble conjugated polymers (WSCPs) that can be processed with a broad thickness range of 5 to 100 nm as efficient electron transporting layers (ETLs) for high-performance PSCs. Space charge limited current and electron spin resonance spectroscopy studies confirm that the presence of amine or ammonium bromide groups on the side chains of the WSCP can n-dope PC71BM at the bulk heterojunction (BHJ)/ETL interface, which improves the electron extraction properties at the cathode. In addition, both amino functional groups can induce self-doping to the WSCPs, although by different doping mechanisms, which leads to highly conductive ETLs with reduced ohmic loss for electron transport and extraction. Ultimately, PSCs based on the self-doped WSCP ETLs exhibit significantly improved device performance, yielding PCEs as high as 9.7% and 10.11% for PTB7-Th/PC71BM and PfiEBT4T-2OD/PC71BM systems, respectively. More importantly, with Pfll3T4T-2OD/PC7IBM BHJ as an active layer, a prominent PCE of over 8% was achieved even when a thick ETL of 100 nm was used. To the best of our knowledge, this is the highest efficiency demonstrated for PSCs with a thick interlayer and light-harvesting layer, which are important criteria for eventually making organic photovoltaic modules based on roll-to-roll coating processes.