Photo-thermo-refractive (PTR) glass is an optical Na–Al–Zn–K–O–F–Br silicate glass doped with Ag, Ce, Sb, and Sn that undergoes photo-thermo-induced volume crystallization of nanosized NaF responsible for localized refractive index changes. PTR glass has found numerous commercial applications, but the intricate mechanism of photo-thermo crystallization is far from being understood. In this paper, we demonstrate that, additional to crystalline phase precipitation, liquid–liquid phase separation (LLPS), i.e. amorphous droplets embedded in the matrix glass, appears concurrently over a wide range of temperatures. The immiscibility temperature is 925°C. The droplet phase is richer in SiO2, rendering the alkali-rich remaining matrix glass a lower glass transition temperature and a higher electrical conductivity than the original glass. The droplet's surface does not catalyze NaF nucleation. Although the effects of LLPS on optical properties of PTR glass are still to be explored, it could contribute to unwanted scattering losses and/or uncontrolled refractive index change. The substantial change in the original glass composition resulting from LLPS should play an important role on NaF crystallization kinetics, and therefore must be considered for an overall understanding of the crystallization mechanism underpinning the refractive index change in PTR glass.