We report Tm3+ doped silica glasses and fiber prepared from mesoporous silica glass by glass phase-separation technology. The Judd–Ofelt parameters and radiation properties of Tm3+ doped silica glasses were calculated and evaluated according to the recorded absorption spectrum. The absorption and emission cross-section, gain spectra and fluorescence lifetime were analyzed. Tm3+ doped large-core double-cladding fiber with a core NA of 0.08 was fabricated by the rod-in-tube method. The measurements show that the fiber has a Tm3+ concentration of 10300 ppm by weight and excellent homogeneity in the fiber core. The 1.8 μm luminescence properties were investigated. It is suggested that the Tm3+ doped silica glass prepared by glass phase-separation technology can be a potential fiber core material to achieve 2 μm fiber laser.