Perovskites have emerged as low-cost, high efficiency photovoltaics with certified efficiencies of 22.1% approaching already established technologies. The perovskites used for solar cells have an ABX₃ structure where the cation A is methylammonium (MA), formamidinium (FA), or cesium (Cs); the metal B is Pb or Sn; and the halide X is Cl, Br or I. Unfortunately, single-cation perovskites often suffer from phase, temperature or humidity instabilities. This is particularly noteworthy for CsPbX₃ and FAPbX₃ which are stable at room temperature as a photoinactive “yellow phase” instead of the more desired photoactive “black phase” that is only stable at higher temperatures. Moreover, apart from phase stability, operating perovskite solar cells (PSCs) at elevated temperatures (of 85 °C) is required for passing industrial norms. Recently, double-cation perovskites (using MA, FA or Cs, FA) were shown to have a stable “black phase” at room temperature. These perovskites also exhibit unexpected, novel properties. For example, Cs/FA mixtures supress halide segregation enabling band gaps for perovskite/silicon or perovskite/perovskite tandems. In general, adding more components increases entropy that can stabilize unstable materials (such as the “yellow phase” of FAPbI₃ that can be avoided using the also unstable CsPbI₃). Here, we take the mixing approach further to investigate triple cation (with Cs, MA, FA) perovskites resulting in significantly improved reproducibality and stability. We then use multiple cation engineering as a strategy to integrate the seemingly too small rubidium (Rb) (that never shows a black phase as a single-cation perovskite) to study novel multication perovskites. One composition containing Rb, Cs, MA and FA resulted in a stabilized efficiency of 21.6% and an electroluminescence of 3.8%. The V_oc of 1.24 V at a band gap of 1.63 eV leads to a very small loss-in-potential of 0.39 V, one of the lowest measured on any PV material indicating the almost recombination-free nature of the novel compound. Polymer-coated cells maintained 95% of their initial performance at 85°C for 500 hours under full illumination and maximum power point tracking. This is a crucial step towards industrialisation of perovskite solar cells. Lastly, to explore the theme of multicomponent perovskites further, molecular cations were revaluated using a globularity factor. With this, we calculated that ethylammonium (EA) has been misclassified as too large. Using the multication strategy, we studied an EA-containing compound that yielded an open-circuit voltage of 1.59 V, one of the highest to date.