In the framework of luminescent rare-earth-doped glasses for near-infrared applications, TiO2-containing inorganic glasses have been recently demonstrated to be a promising alternative to commercially used high-phonon SiO2-based glasses. This study investigates the effect of TiO2 concentration on the near-infrared spectroscopic properties of Yb3+ ions in multicomponent titanate–germanate glasses. A series of glass samples in the xTiO2-(60−x)GeO2-BaO-Ga2O3-Yb2O3 system (x ranging from 0 to 50 mol%) were synthesized using the melt-quenching technique. X-ray diffraction analysis confirmed the fully amorphous nature of the fabricated titanate–germanate samples. Fundamental spectroscopic properties of Yb3+-doped titanate–germanate system consisting of absorption spectra, near-IR emission spectra, and luminescence decay curves have been determined based on measurement using optical spectroscopy. The intensity of the emission band at 1 µm due to the 2F5/2 → 2F7/2 laser transition of Yb3+ ions increases by over 2.3-fold (TiO2 as the network former) compared to a barium gallo-germanate sample without TiO2. Our previous studies indicate that Yb3+-doped titanate–germanate glass is a promising optical material and could be successfully applied to laser technology.