Targeting the huge unused bandwidth (BW) of modern telecommunication networks, Bi/Er co-doped silica optical fibers (BEDFs) have been proposed and developed for ultra-broadband, high-gain optical amplifiers covering the 1150–1700 nm wavelength range. Ultrabroadband luminescence has been demonstrated in both BEDFs and bismuth/erbium/ytterbium co-doped optical fibers (BEYDFs) fabricated with the modified chemical vapor deposition (MCVD) and in situ doping techniques. Several novel and sophisticated techniques have been developed for the fabrication and characterization of the new active fibers. For controlling the performance of the active fibers, post-treatment processes using high temperature, γ-radiation, and laser light have been introduced. Although many fundamental scientific and technological issues and challenges still remain, several photonic applications, such as fiber sensing, fiber gratings, fiber amplification, fiber lasers, etc., have already been demonstrated.