Rare‐earth‐based all‐inorganic glass‐ceramics have exhibited an important role in the field of optoelectronics. However, the research of organo–inorganic hybrid rare‐earth halide glass which can be produced at low temperatures is still in the blank stage. In this paper, we report for the first time on novel amorphous organic–inorganic hybrid rare‐earth‐based halide luminescent glasses, Bzmim3LnCl6 (Bzmim = 1‐benzyl‐3‐methylimidazolium; Ln3+ = Tb3+, Eu3+), and realize tunable multicolor photoluminescence emission. By adjusting the ratio of Tb3+: Eu3+ within the Bzmim3LnCl6 glass, we have successfully induced controllable radioluminescence properties ranging from green to red under X‐ray irradiation. Notably, these amorphous organic–inorganic hybrid rare‐earth glasses exhibit remarkable sensitivity to variations in X‐ray dose, suggesting promising applications in the field of passive color visualization radiation detection. Furthermore, the Bzmim3TbCl6 glass demonstrates exceptional light transmittance greater than 85% across the 480–800 nm range, which results in superior spatial resolution in X‐ray imaging (>25 lp mm–1). These findings not only provide a good example for the design and development of hybrid rare‐earth‐based halide glasses, but also hold great potential for applications in detection, sensing, illumination, and display technologies.