Direct comparison between perovskite-structured hybrid organic–inorganic methylammonium lead bromide (MAPbBr₃) and all-inorganic cesium lead bromide (CsPbBr₃), allows identifying possible fundamental differences in their structural, thermal and electronic characteristics. Both materials possess a similar direct optical band gap, but CsPbBr₃ demonstrates a higher thermal stability than MAPbBr₃. In order to compare device properties, we fabricated solar cells, with similarly synthesized MAPbBr₃ or CsPbBr₃, over mesoporous titania scaffolds. Both cell types demonstrated comparable photovoltaic performances under AM1.5 illumination, reaching power conversion efficiencies of ∼6% with a poly aryl amine-based derivative as hole transport material. Further analysis shows that Cs-based devices are as efficient as, and more stable than methylammonium-based ones, after aging (storing the cells for 2 weeks in a dry (relative humidity 15–20%) air atmosphere in the dark) for 2 weeks, under constant illumination (at maximum power), and under electron beam irradiation.