Iron-rich phosphate glasses with nominal Fe/P ratios between 1.0 and 1.6 were prepared by a rollerquenching technique. The critical cooling rates (CCR) for glass formation were estimated by differential thermal analysis and found to be in the range of 103-104 °C/s for the iron-rich melts, compared to 1-10 °C/s for conventional iron phosphate melts with nominal Fe/P ratios near 0.50. The Fe(II)/Fetotal fraction in the quenched glasses increases with melt time and temperature, and ranges between 0.30 and 0.55 for theglasses studied. Raman spectroscopy indicates that the structures of the iron-rich phosphate glasses are based on isolated orthophosphate tetrahedra, similar to what are found in α-FePO 4. © 2010 Elsevier B.V. All rights reserved.