We present some of our research activities dedicated to doped silica-based optical fibers, aiming at understanding the spectral properties of luminescent ions, such as rare-earth and transition metal elements. The influence of the local environment on dopants is extensively studied: energy transfer mechanisms between rare-earth ions, control of the valence state of chromium ions, effect of the local phonon energy on thulium ions emission efficiency, and broadening of erbium ions emission induced by oxide nanoparticles. Knowledge of these effects is essential for photonics applications.