Organic–inorganic hybrid metal halides are widely used in X‐ray detection and imaging due to their high X‐ray absorption efficiency, ease of synthesis, and efficient luminescence. However, the issue of lead toxicity remains a concern. In this study, non‐toxic, 0D 2,2′‐(Ethylenedioxy)bis(ethylamine) manganese (II) bromide (EDBEMnBr4) is synthesized using the simple mechanical grinding method and the solution method that exhibits intense green emission at ≈525 nm. Moreover, the change of structure under the influence of temperature and water significantly affects its fluorescence color under UV light. Scintillator materials with and without moisture exposure showed spatial resolutions of 7 and 4 lp mm−1, and low detection limits of 4.62 and 5.25 µGyair s−1, respectively, meeting medical industry standards (<5.5 µGyair s−1). Furthermore, based on the apparent change in luminescence color triggered by moisture for EDBEMnBr4, a preliminary attempt is made to apply it to humidity monitoring showing that the boundary of color change has a good linear dependence on humidity and time. This work provides new opportunities for Mn‐based metal halides in both X‐ray detection as well as moisture detection.