Localized sub-micrometer-scale visible and near-IR fluorescence structures have been achieved in three-dimension (3D) thanks to femtosecond laser-activated photochemistry of Bismuth in a Bismuth-doped phosphate glass. These structures exhibit high fluorescence contrast with good spatial resolution with spectral emission in the red and near-IR ranges. These fluorescence properties arise from femtosecond laser-induced multi-photon absorption and the creation of free electrons, which activates local redox reactions of Bi3+ that allow for the dose-dependent formation of low valence Bismuth ions such as Bi2+ and Bi+. These new species promote not only new selective fluorescence emission properties in the VIS and near-IR spectral range but also co-localized positive refractive index changes. The thermal treatment of 3D patterns evidences the possibility of Bismuth cluster formation with good thermal stability up to the glass temperature transition. These observations open the way for laser-inscribed photonic integrated circuits for potential laser amplification devices in the second telecommunication windows around 1.3 μm.