We report an experimental analysis of new hafnia-yttria-alumina-silica glass based fiber doped with bismuth (Bi), with absorption/fluorescence spectra along with resonantabsorption saturation, fluorescence lifetime, and gain, all adherent to Bi-related active centers (BACs), being measured at laser-diode excitation @ 908, 976, 1069, and 1120 nm, matching the NIR BACs' band. The found spectral laws reveal the optimal on excitation wavelength fluorescence, resonant-absorption bleaching, and gain capacities of the fiber, useful for applications at diode pumping. Besides, we report, for the first time to the best of our knowledge, a new resonant-absorption band of BACs in mid-IR (~2.1 µm) in the fiber, effectively bleached under the action of low-power in-band excitation, and provide the reasons for its association with co-doping the fiber with hafnium.