This work presents a detailed study on near-infrared and mid-infrared fluorescence emissions with five sets of Tm3+-doped 75GeS2–15Ga2S3–10CsI chalcohalide glass. They are prepared in normal or water drying process. Based on the diffusion-limited relaxation calculation, a detailed investigation is put forward to obtain efficient near-infrared or mid-infrared fluorescence emissions of Tm3+ on the effect of H2O on the Tm3+ fluorescence. Detailed investigations are given to the interacted energy transferring processes between rare-earth, impurities and vibrating phonons with the appearance of fluorescence quenching, along with Tm3+, H2O concentrations varying and energy gaps forming. The radioactive properties are analyzed using compensated diffusion-limited relaxation calculation method, and the near-IR and mid-IR fluorescence properties are evaluated in detail with experimental and theoretical analysis.