This chapter is devoted to new group of luminescence materials which are now being actively investigated: glassy semiconductors (chalcogenicle glasses) doped with rare-earth ions (REI). We enumerate the unique properties of this group of materials, which attract interest for prospective use as a matrix for rare-earth doping. We describe the glassy systems, which are the most promising for the synthesis of effective luminescence materials. This chapter also contains results of investigations of the structure and composition of the nearest neighbors of REI in chalcogenicle glasses as well as Stokes and anti-Stokes luminescence, including a specific method of REI excitation via optical pumping using band-band absorption of matrix.