In this paper, the impact of B2O3, ZnO and TiO2 addition on the structure, Er3+ luminescence and crystallization of glasses in the Er2O3P2O5CaOSrONa2O glass system is reported. The thermal properties of the as-prepared glasses were recorded using a DTA and the structure of the glasses prior to and after heat treatment was analyzed using Raman and IR spectroscopies. Crystallization of the glass after heat treatments was confirmed by the presence of sharp peaks in the XRD patterns. Based on the XRD pattern, two different crystalline phases are suspected to precipitate, the composition of which depends on the glass composition. From the spectroscopic properties of the glasses, the Er3+ ions are not suspected to be incorporated in the crystals.