Large, strain free, single crystals of high optical quality selected from the IB-VB-VIB and IIIB-VB-VIB ternary chalcogenide groups, having a single stable solid phase from room temperature to the melting point of the crystal and vice-versa, are synthesized by (1) placing stoichiometric quantities of the compound constituents with 3% excess VIB constituent in a two part, sublimation-reaction fused silica tube, the VB constituents being placed in sublimation part, and the remaining constituents being placed in the reaction part, and evacuating and sealing the tube, (2) subliming and purifying the VB constituent and condensing it in the reaction part, which is then cooled and sealed from the sublimation part, (3) reacting, uniting and slowly cooling the reaction part constituents, (4) placing the reacted constituents in fused silica growth tube, which is evacuated, backfilled with helium, and sealed, (5) forming a melt in the upper part of a two part furnace and lowering at about 1.8 mm/hr. through a greater than 100.degree.C temperature gradient, (6) annealing the single crystal in the lower furnace part about one-half the melting point temperature and cooling it to room temperature at about 5.degree.C/hr., and (7) removing the crystal by dissolving the tube in hydrofluoric acid.