The luminous efficiency of inorganic white light‐emitting diodes, to be used by the next generation as light initiators, is continuously progressing and is an emerging interest for researchers. However, low color‐rendering index (Ra), high correlated color temperature (CCT), and poor stability limit its wider application. Herein, it is reported that Sm3+‐ and Eu3+‐doped calcium scandate (CaSc2O4 (CSO)) are an emerging deep‐red‐emitting material with promising light absorption, enhanced emission properties, and excellent thermal stability that make it a promising candidate with potential applications in emission display, solid‐state white lighting, and the device performance of perovskite solar cells (PSCs). The average crystal structures of Sm3+‐doped CSO are studied by synchrotron X‐ray data that correspond to an extremely rigid host structure. Samarium ion is incorporated as a sensitizer that enhances the emission intensity up to 30%, with a high color purity of 88.9% with a 6% increment. The impacts of hosting the sensitizer are studied by quantifying the lifetime curves. The CaSc2O4:0.15Eu3+,0.03Sm3+ phosphor offers significant resistance to thermal quenching. The incorporation of lanthanide ion‐doped phosphors CSOE into PSCs is investigated along with their potential applications. The CSOE‐coated PSCs devices exhibit a high current density and a high power conversion efficiency (15.96%) when compared to the uncoated control devices.