The glass formation and crystallization of liquid-quenched (GeSe2)100-y/(Sb2Te3)y alloys was investigated by means of differential scanning calorimetry, X-ray diffraction and optical and scanning electron microscopy. By water quenching glasses are obtained from compositions in the range 5≲y≲30. Qualitative parametrization of glass-forming tendency gives, as best glass formers, alloys with y≅20. Crystallization on heating proceeds in one stage for glasses with y≲20 and in two stages for those with greater Sb2Te3 content. For compositions lying in the GeSe2 primary crystallization region crystals appear preferentially at the surface of the sample, but for the other compositions (24≲y≲30) the crystals emerge in the bulk and often develop in spherulitic or axialitic form. © 1984 Chapman and Hall Ltd.