The doping of nanoporous glass (PG) is a prospective technique for producing bismuth (Bi)-doped optical fibers. The refractive index of sintered PG is lower than pure silica glass because of PG high residual content of boron (2 to 3 at.%). This fact impedes the choice of fiber cladding for building a light-guiding structure. We have chosen the microstructured optical fiber with the core from Bi-doped nanoporous glass to overcome this problem. We have studied the glass composition and controlled the luminescent properties of bismuth active centers at each step of the fiber fabrication. The PG is suitable for the production of microstructured fibers.