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Glasses from a complex SiO2-Al2O3-P2O5-CaO-CaF2 glass series, known as 'ionomer glasses' were investigated. For comparison, a sodium-boro-silicate (s-b-s) glass system, which is known to undergo amorphous phase separation was also investigated. Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and BET surface area and pore distribution analysis were the principal analytical techniques used in this study. SEM analysis of the ionomer glass compositions revealed smooth spherical droplets of 2–15 nm while the background morphology appeared rough and speckled. A classic interconnected structure was observed for the s-b-s glass. EDX analysis of the s-b-s glass confirmed that the sodium-borate phase was removed by leaching with 0.3 M HNO3, leaving behind a silica-rich structure. EDX analysis of ionomer glasses leached with 10% NaOH showed that the calcium and phosphate phases were being removed, although not to completion. For the base s-b-s glass a surface area of m 82 g−1 was recorded. However, the base glass after extraction with 0.3 M HNO3 of the sodium borate rich phase gave a BET surface area of 330 m2 g−1 indicating that it had already undergone phase separation on quenching from the melt, giving rise to a fine scale interconnected structure. The leached s-b-s glasses exhibited type 4 adsorption/desorption isotherms characteristic of mesoporous materials. Glasses which had been heat treated at 580°C for 4 h exhibited a surface area of 62 m2 g−1. This indicates that the as-quenched glass is already phase separated and that the phase separated microstructure is coarsening on heat treatment. A surface area of 4 m2 g−1 was measured for the base ionomer glasses. After leaching with 10% NaOH this value rose 10-fold with a maximum surface area of 44.1 m2 g−1 being recorded. The ionomer glasses also exhibited adsorption/desorption isotherms characteristic of mesoporous materials.