In this study, a high-performance inverted polymer solar cell (PSC) has been fabricated by incorporating a zinc oxide (ZnO)/light-harvesting complex II (LHCII) stacked structure as the cathode interlayer. The LHCII not only smoothens the film surface of ZnO, improves the contact between ZnO and the photoactive layer, but also suppresses the charge carrier recombination at the interface, hence all the device parameters of PTB7-based solar cells are simultaneously improved, yielding higher power conversion efficiency (PCE) up to 9.01% compared with the control one (PCE 8.01%). And the thin LHCII modification layer also presents similar positive effects in the PTB7-Th:PC₇₁BM system (PCE from 8.31% to 9.60%). These results put forward a facile approach to the interfacial modification in high-performance PSCs and provide new insight into developing and utilizing inexpensive and environmentally friendly materials from the fields of biological photosynthesis.