Abstract: In order to study the changes of the structure and chemical durability with Fe/P mole ratio(r(Fe/P)), a series of P₂O₅-Fe₂O₃-Al₂O₃-Na₂O-ZrO₂ glass-ceramic samples with different Fe/P mole ratios were prepared by the melting-quenching method. X-ray diffraction was used for phase analysis, and Raman spectroscopy, X-ray photoelectron spectroscopy and M-ssbauer spectroscopy were used for structural analysis. n(Fe³⁺)/(n(Fe²⁺)+n(Fe³⁺)) mole ratios increase with the increase of Fe/P mole ratio when the Fe/P mole ratio is less than 0.18. When the Fe/P mole ratio is between 0.18 and 0.32, n(Fe³⁺)/(n(Fe²⁺)+n(Fe³⁺)) fluctuates around 60%. The samples with Fe/P mole ratio between 0.2 and 0.3 have the best chemical durability and relatively low crystal fraction.