So far, most techniques for modifying perovskite solar cells (PSCs) focus on either the perovskite or electron transport layer (ETL). For the sake of comprehensively improving device performance, a dual-functional method of simultaneously passivating trap defects in both the perovskite and ETL films is proposed that utilizes guidable transfer of Eu3+ in SnO2 to perovskite. Europium ions are distributed throughout the SnO2 film during the formation process of SnO2, and they can diffuse directionally through the SnO2/perovskite interface into the perovskite, while most of the europium ions remain at the interface. Under the synergistic effect of distributed Eu3+ in the SnO2 and aggregated Eu3+ at the interface, the electron mobilities of ETLs are evidently improved. Meanwhile, diffused Eu3+ ions passivate the perovskite to reduce trap densities at the grain boundaries, which can dramatically elevate the open-circuit voltage (Voc) of PSCs. Finally, the mainly PSCs coated on SnO2:Eu3+ ETL achieve a power conversion efficiency of 20.14%. Moreover, an unsealed device degrades by only 13% after exposure to ambient atmosphere for 84 days.