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Perovskite solar cells were fabricated with SnO₂ thin films as a window layer and electron transport layer by thermal evaporation. Fundamental characteristics of SnO₂ thin films to determine the performance of solar cells were investigated in an optical and electrical manner, varying annealing temperatures. It is found the crystallinity and the presence of localized energy states play a key factor to control the properties of SnO₂. In addition, XPS was used to confirm the stoichiometry of the SnO₂ thin films, indicating a better charge collection on the annealed SnO₂ samples. The SnO₂ thin films annealed at 300 °C exhibited desirable optical and electrical properties for the enhanced performance of solar cells. The results show that thermally evaporated SnO₂ thin films can be precisely engineered and controlled for mass production and more practical industrialization of perovskite solar cells.