We report on both the intrinsic and the extrinsic stability of a formamidinium lead bromide [CH(NH$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$)$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$PbBr$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$ = FAPbBr$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$] perovskite solar cell that yields a high photovoltage. The fabrication of FAPbBr$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$ devices, displaying an outstanding photovoltage of 1.53 V and a power conversion efficiency of over 8%, was realized by modifying the mesoporous TiO2-FAPbBr$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$ 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 TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ films, PDS reveals that the TiO2-FAPbBr$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$ interface exhibits low energetic disorder, and the emission dynamics showed that electron injection from the conduction band of FAPbBr$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$ into that of mesoporous TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ is faster than for the untreated scaffold. Moreover, compared to the device with pristine TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$, the charge carrier recombination rate within a device based on lithium-treated TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ 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$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$ 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 = ∼60 °C). The demonstration of high photovoltage, a record for FAPbBr$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$, together with robust stability renders our work of practical significance.