In this work, W-doped TiO2, was successfully fabricated, as electron transport layer (ETL) in perovskite solar cells (PSCs) via low-temperature solution-processed method, whose outstanding performances were verified. The experimental results reveal that, W6+ was doped into the TiO2 lattice successfully. The improved ETL exhibit significantly improved on conductivity, transport and extraction of photo-generated carriers and less trap-state density as compared with the pristine TiO2 films. Meanwhile, strengthening the velocity of carrier and collection of sufficient charge can efficiently increase short-circuit current (JSC) which favor an improved fill factor (FF) and a higher power conversion efficiency (PCE). Our optimized cation–anion-mixed PSC based on W-doped TiO2 has achieved an efficiency of 18.85%. This improved PCE is almost 28.1% higher than that of the pure TiO2. This study provides a promising approach to design metal-doped TiO2 for fabricating high-performance perovskite solar cells.