Because of its high conductivity, wide bandgap, and excellent photostability, tin oxide (SnO2) has long been recognized as an electron transport layer (ETL) in organic solar cells (OSCs). However, the energy‐level mismatch between the work function (WF) of SnO2 and the lowest unoccupied molecular orbital level of Y‐series non‐fullerene acceptors (NFAs), along with the abundance of surface defects on SnO2, have limited its widespread application as ETLs in OSCs. Herein, we introduce a novel approach utilizing urea‐functionalized polyethyleneimine (PEI) materials called u‐PEIs for modifying SnO2. This modification, which serves dual purposes of WF modulation and surface‐defect passivation, can mitigate the energy barriers of SnO2/Y‐series NFA and increase the conductivity of the SnO2 film. PM6:Y6‐based OSCs with u‐PEI‐modified SnO2 (SnO2:u‐PEI) ETLs exhibited a remarkable efficiency of 16%, which significantly exceeded that (13.5%) achieved with bare SnO2‐based OSCs, along with outstanding photo‐ and thermal‐ stability. This study confirms the efficacy of urea‐functionalized PEI for efficient and stable OCSs, paving the way for SnO2 applications.This article is protected by copyright. All rights reserved.