A fluorosilicate (FS) nano-crystallized glass ceramic (NGC) is one of the most commonly used gain materials for applications in optical devices due to its excellent thermal stability as well as high-efficiency luminescence. However, FS glass can hardly be used to prepare NGC fibers due to its high preparation temperature. Here, a series of low-temperature fluoro-borosilicate (FBS) glasses were designed for the fabrication of active NGC fibers. By modulating B2O3, the preparation temperature of FBS glass was reduced to 1050 °C, and the crystallization in FBS NGCs was more controllable than in FS NGC. The crystallization of the impure phase was inhibited, and single-phase rare earth (RE)-fluoride nanocrystals were controllably precipitated in the FBS NGCs. The 40Si-20B FBS NGC not only exhibited a higher optical transmittance, but the luminescence efficiency was also much higher than traditional FS NGCs. More importantly, NGC fibers were successfully fabricated by using the designed FBS glass as core glass. Nanocrystals were controllably precipitated and greatly enhanced, and upconversion luminescence was observed in NGC fibers. The designed FBS NGCs provided high-quality optical gain materials and offered opportunities for fabricating a wide range of NGC fibers for multiple future applications, including fiber lasers and sensors.