In organic solar cells, interfacial materials play essential roles in charge extraction, transportation, and collection. Currently, highly efficient and thickness-insensitive interfacial materials are urgently needed in printable large area module devices. Herein, water/alcohol-soluble conjugated polyelectrolyte PFNBT-Br, with medium bandgap based on benzothiadiazole, are doped by two alkali metal sodium salts, NaH 2 PO 2 , Na 2 C 2 O 4 with different counter anions, to pursue high efficiency and thickness-insensitive electron-transport layers. Results show that the doping of electron-transport material can effectively promote the performance of the devices. Moreover, electron-transport layers doped by these salts with different counter anions show different behaviors in performances. Among which, the salt with oxalate anion C 2 O 4 2− (also named Ox 2− ) shows much better device performance than the salt with hypophosphite anion (H 2 PO 2 − ), especially under the thick film condition (e.g., 50 nm). The greatly enhanced performances of interfacial material doped by Ox 2− are due to reduced series resistance between the active layer material and the electrode, reduced dark-current, improved charge transport, and extraction efficiency, and decreased charge recombination for the devices at thick-film condition. These results demonstrated that n-doping could be a great potential strategy for making thickness-insensitive interfacial layers, besides, the performances can be further improved by carefully selecting salts.