Linear sweep voltammograms and absorption spectra were recorded in Na2O·2.5 SiO2 containing about 1 wt% Fe at some temperatures ranging from 600°C to 1000°C. The reduction peaks which are observed in the melt at 600°C disappear at 1000°C. The absorption spectra obtained at high temperature are characteristic by a displacement of the charge transfer band and of the band related to octahedral Fe(II) towards higher wavelengths. No remarkable change in the Fe(III)‐Fe(II) redox equilibrium and in the coordination of the Fe(II) has been observed between 600°C and 1000°C.