Photodetectors are widely employed as fundamental devices in optical communication, automatic control, image sensors, night vision, missile guidance, and many other industrial or military fields. Mixed-cation perovskites have emerged as promising optoelectronic materials for application in photodetectors due to their superior compositional flexibility and photovoltaic performance. However, their application involves obstacles such as phase segregation and poor-quality crystallization, which introduce defects in perovskite films and adversely affect devices’ optoelectronic performance. The application prospects of mixed-cation perovskite technology are significantly constrained by these challenges. Therefore, it is necessary to investigate strategies that combine crystallinity control and defect passivation to obtain high-quality thin films. In this study, we incorporated different Rb+ratios in triple-cation (CsMAFA) perovskite precursor solutions and studied their effects on crystal growth. Our results show that a small amount of Rb+was enough to induce the crystallization of the α-FAPbI3phase and suppress the formation of the yellow non-photoactive phase; the grain size increased, and the product of the carrier mobility and the lifetime (μτ) improved. As a result, the fabricated photodetector exhibited a broad photo-response region, from ultraviolet to near-infrared, with maximum responsivity (R) up to 11.8 mA W−1and excellent detectivity (D*) values up to 5.33 × 1011Jones. This work provides a feasible strategy to improve photodetectors’ performance via additive engineering.