In this paper, we performed a comparative spectroscopic analysis of Tm3+-doped glasses based on GeO2-BaO-Ga2O3 (GBG) and TiO2-GeO2-BaO-Ga2O3 (TGBG) to achieve broadband luminescence at 1.8 μm. Glasses were prepared at different doping concentrations (0.05 mol% and 1mol%) in order to investigate the effect of Tm3+ ions as well as host composition (GeO2:TiO2 molar ratios) on near-IR luminescence properties. We report on the hypersensitivity of the transition 3H6 → 3F4 of Tm3+ in a series of titanate-germanate glasses, which was shifted to longer wavelengths with increasing TiO2 concentration. The relative intensity of the main near-IR emission band corresponding to the 3F4 → 3H6 (1.8 μm) transition of Tm3+ was 4.8-fold enhanced for glass with molar ratio GeO2:TiO2 = 1:5 compared to GBG glass system. We observed the luminescence quenching phenomena for samples containing more than 0.5 mol% of Tm3+ ions. The calculated spectroscopic parameters, such as measured luminescence lifetime (τm) and the quantum efficiency (η), were discussed and compared to the different laser glasses. Importantly, luminescence decay curves have been examined using the Inokuti-Hirayama model. Additionally, the correlation between optical properties and local structure in glasses was well evidenced by Raman spectroscopy. The proposed strategy, in combination with various chemical composition of glass host activated by various Tm2O3 concentration, might be beneficial for modern near-infrared photonics.