Scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy and X-ray diffraction (XRD) analyses were used to characterise the microstructure and chemical composition of a glass and a glass-ceramic material obtained from incinerator filter fly ash. Although the as-quenched material (vitrified fly ash) was amorphous under the detection limits of XRD, a dispersion of droplets indicating glass-in-glass phase separation was observed. In the glass-ceramic material (crystallised vitrified fly ash), crystals belonging to the pyroxene group and spinels were identified. The microstructure of the glass-ceramic consisted of crystals embedded in an amorphous glassy phase. The crystalline phases contain a higher amount of metallic elements (e.g. Al, Cr, Fe, Ni and Zn and most probably also other heavy metals) than the residual glassy phase. A change of composition of the residual glass phase in the glass-ceramic product, in comparison with the parent glass, is considered to explain, in comparative terms, the higher toxic potential of the glass-ceramic over the glass. The present results demonstrate that for an accurate assessment of the correlation between toxicity, release of hazardous compounds and microstructure, high-resolution characterisation techniques must be employed. In this context, the effect of crystallisation on the chemical durability of the products remains as an important area for further research.