Perovskite solar cells (PSCs) based on cesium (Cs)- and rubidium (Rb)-containing perovskite films show highly reproducible performance; however, a fundamental understanding of these systems is still emerging. Herein, this study has systematically investigated the role of Cs and Rb cations in complete devices by examining the transport and recombination processes using current-voltage characteristics and impedance spectroscopy in the dark. As the credibility of these measurements depends on the performance of devices, this study has chosen two different PSCs, (MAFACs) Pb(IIBr)(3) (MA = CH3NH3+, FA = CH(NH2)(2)(+)) and (MAFACsRb) Pb(IIBr)(3), yielding impressive performances of 19.5% and 21.1%, respectively. From detailed studies, this study surmises that the confluence of the low trap-assisted charge-carrier recombination, low resistance offered to holes at the perovskite/2,2', 7,7'-tetrakis(N, N-di-p-methoxyphenylamine)- 9,9-spirobifluorene interface with a low series resistance (R-s), and low capacitance leads to the realization of higher performance when an extra Rb cation is incorporated into the absorber films. This study provides a thorough understanding of the impact of inorganic cations on the properties and performance of highly efficient devices, and also highlights new strategies to fabricate efficient multiple-cation-based PSCs.