LAUSR

As an electron transport layer (ETL) widely used in organic solar cells (OSCs), ZnO has problems with energy level mismatch with the active layer and excessive defects on the ZnO surface, which can reduce the efficiency of OSCs. Here, ZnO/ZrSe2 composite is fabricated by modifying ZnO with 2D ZrSe2. The XPS and first‐principles calculation (FPC) show that ZnO obtains electrons from ZrSe2 and forms interfacial dipoles toward the active layer, which decreases the work function of ZnO, thus reducing the interface barrier and favoring the collection of electrons in OSCs. At the same time, after ZrSe2 modification, the oxygen vacancy density on the ZnO surface decreases, thus improving the conductivity of ZnO. More importantly, the femtosecond transient absorption (Fs‐TA) shows that ZrSe2 selectively traps holes from the active layer, which prevents the holes from entering the ZnO, thereby reducing the probability of electron recombination. Finally, ZnO/ZrSe2 composite is used as a novel ETL in OSCs with PBDB‐T: ITIC, PM6:Y6 and PM6: L8‐BO as active layers, and obtaining 12.09%, 16.34%, and 18.24% efficiency, respectively. This study provides a method for the interface modification of ZnO, and further investigates the role of 2D nanosheets in the interface modification.