Abstract Homogeneous BaO.Fe 2O 3.Na 2O glass containing 60% Fe 2O 3 is prepared by splat cooling technique. X-ray diffraction reveals the presence of a few small βNaFeO 2 crystallites in a glassy matrix. DTA studies show that βNaFeO 2 cristallizes first and BaFe 12O 19 next. In the temperature range 130K < T < 400K this glass shows Curie-Weiss behaviour with large negative Weiss constant. The magnetic susceptibility measurements below 130K exhibit a broad maximum near 90–110K. Mössbauer study reveals that the glass mainly consists of tetrahedral network of Fe 3+O 4 and a hyperfine structure at low temperature; magnetic ordering temperature estimated is about (125 ± 5)K.