Crystallization behavior, structure and properties of the glasses in SrO–Fe2O3–P2O5 ternary system, with the content of P2O5 fixed to be 60, 50 and 40 mol%, were studied systematically. For vitreous samples, thermal expansion coefficients (TEC) and characteristic temperature were obtained by using a thermal dilatometer, while their thermal stability was examined by using a differential scanning calorimeter (DSC). Accordingly, their heat treatment schedules were determined. Furthermore, their chemical durability was characterized according to the dissolution rate (DRwater) in distilled water at 90 °C. Glass forming region of the SrO–Fe2O3–P2O5 ternary system at 1250 °C has been identified. It was found that crystallization behavior, crystalline phase compositions, structure and properties of the samples are closely related to the ratios of O/P and Fe/P. Specifically, the iron phosphate glasses were explored as the host matrices to immobilize high-level radioactive wastes (HLWs) with high contents of 90Sr.