Glass composition of 6Na2O 22B2O3·70SiO2·2Cr2O3 is studied by scanning electron microscopy, X‑ray powder diffractometry (XRPD), and differential thermal analysis, depending on the duration of heat treatment at a temperature of 550°C. It is established that during heat treatment for 24–96 h, a phase separation structure with interpenetrating phases is formed in the studied glass, and a crystalline phase of eskolaite—Cr2O3 is also formed. With the maximum heat treatment duration of 96 h, cristobalite is formed in the bulk of the glass, which is accompanied by a decrease in the glass transition temperature of the low-viscosity phase. In this case, the intensity of eskolaite peaks decreases. Cr2O3 and SiO2 crystallize apparently due to the substance of the low-viscosity phase.