A crystallization study of the TeO 2 -InF 3 glass system shows that the specific glass composition 75TeO 2 -25InF 3 stabilizes a novel cubic anti-glass phase within the glass matrix upon heat treatment. This peculiar crystalline phase also called "glass of anions" exhibits an interesting order/disorder coexistence, that is, a long-range cation order but with a highly disordered anion sublattice. The thermal properties, structure and microstructure of the parent glass and corresponding glass-ceramics have been studied. Finally, the luminescence of Yb 3+ -doped glass-ceramics has been characterized, which confirmed the presence of the disordered anti-glass phase.