Active layer morphology optimization and electrode buffer layer interface modification are commonly used strategies in improving the performance of polymer solar cells (PSCs). In this study, we prepared PTB7: PC71BM bulk heterojunction PSCs with 1,8-diiodooctane (DIO) and polyethylene glycol (PEG) additives, and studied the influence of binary additives on exciton dissociation, charge transport and charge extraction. DIO facilitates donor/acceptor phase separation for efficient exciton dissociation and charge transport. The migration of PEG from active layer to the PEDOT:PSS layer improves the crystallinity of PTB7, optimizes charge transport pathway, and enhances the conductivity of PEDOT:PSS layer. With the combined advantages of binary additives in active layer morphology optimization and anode buffer layer modification, the device exhibits a high shortcircuit current density of 20.03 mA/cm(2) and an improved power conversion efficiency. Binary additive provides a promising method to optimize active layer morphology and improve interfacial buffer layer of PSCs simultaneously.