Flexible perovskite solar cells are new technology-based products developed by the global solar industry and are promising candidates for realizing a flexible and lightweight energy supply system for wearable and portable electronic devices. A critical issue for flexible perovskite solar cells is to achieve high power conversion efficiency (PCE) while using low-temperature solution-based technology for the fabrication of a compact charge collection layer. Herein, we innovatively introduce niobium ethoxide as a precursor additive to TiO₂ NCs, which allows realization of an Nb₂O₅–TiO₂ electron transport layer (ETL). The presence of Nb₂O₅ remarkably enhances electron mobility and electrical conductivity of the ETLs. In addition, uniform perovskite films are prepared by an annealing-free solution-based method. The excellent performance of the cell is attributed to its smooth film surface and high electron mobility, and performance is verified by the effective suppressions of charge recombination and time-resolved photoluminescence. PCEs of 15.25% and 13.60% were obtained for rigid substrates (glass/fluorine-doped tin oxide) and an indium tin oxide/PET (poly(ethylene terephthalate)) flexible substrate by using a totally room-temperature solution-processing method, respectively.