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High-performance electron transport layer (ETL) anode generally needs to form a uniform dense layer with suitable conduction band position and good electron transport properties. The TiO2 photoanode is primarily applied as the ETL because it is low-cost, has diverse thin-film preparation methods and has good chemical stability. However, pure TiO2 is not an ideal ETL because it lacks several important criteria, such as low conductivity and conduction band mismatch with compositional-tailored perovskite. Thus, TiO2 is an inefficient photo-anode or ETL for high-performance perovskite devices. In this study, sulfur as dopant in the TiO2 photo-anode thin film is used to fabricate solid-state planar perovskite solar cells in relatively high humidity (40–50%). The deposited S-doped thin film improves the power conversion efficiency (PCE) of the device to 6.0%, with the un-doped TiO2 producing a PCE of 5.1% in the best device. Improvement in PCE is due to lower recombination and higher photocurrent density, resulting in 18% increase in PCE (5.1–6.0%).