We report on both the intrinsic and the extrinsic stability of a formamidinium lead bromide [CH(NH2)(2)PbBr3 = FAPbBr(3)] perovskite solar cell that yields a high photovoltage. The fabrication of FAPbBr(3) devices, displaying an outstanding photo voltage of 1.53 V and a power conversion efficiency of over 8%, was realized by modifying the mesoporous TiO2-FAPbBr(3) interface using lithium treatment. Reasons for improved photovoltaic performance were revealed by a combination of techniques, including photothermal deflection absorption spectroscopy (PDS), transient-photovoltage and charge-extraction analysis, and time-integrated and time-resolved photoluminescence. With lithium-treated TiO2 films, PDS reveals that the TiO2-FAPbBr(3) interface exhibits low energetic disorder, and the emission dynamics showed that electron injection from the conduction band of FAPbBr(3) into that of mesoporous TiO2 is faster than for the untreated scaffold. Moreover, compared to the device with pristine TiO2, the charge carrier recombination rate within a device based on lithium-treated TiO2 film is 1 order of magnitude lower. Importantly, the operational stability of perovskites solar cells examined at a maximum power point revealed that the FAPbBr(3) material is intrinsically (under nitrogen) as well as extrinsically (in ambient conditions) stable, as the unsealed devices retained over 95% of the initial efficiency under continuous full sun illumination for 150 h in nitrogen and dry air and 80% in 60% relative humidity (T = similar to 60 degrees C). The demonstration of high photovoltage, a record for FAPbBr(3), together with robust stability renders our work of practical significance.