The present invention discloses one kind of ultralow thermal expansion devitrified glass used for reflector, planar mirror, template and other precise optical elements. It has the material composition of: SiO2 47.2-49.1(in wt%, the same as below),Al2O3 27.6-29.0,Sb2O3 0.78-0.82,As2O3 0.30-0.35,BaO 2.98-3.05,ZnO 2.00-2.05, CaO 2.28-2.33,MgO 0.5-1.0,Li2O 7.1-7.5,P2O5 4.0-4.4,ZrO2 1.2-1.7 and TiO2 1.4-1.5 . The technological process includes the following steps: mixing the components, high temperature smelting in high temperature quartz-ceramic crucible at 1580-1630 deg.c, tapping at 1450 deg.c, forming, inspection, nucleating at 660-690 deg.c, crystallizing at 690-720 deg.c, precise annealing at 640-540 deg.c.