Quaternary Ag(2)O-CaO-Bi(2)O(3)-B(2)O(3) glasses and glassceramics are investigated with regard to release behaviour and local structure. The dissolution behaviour in water and physiological serum shows that the cations are released rapidly or gradually and points out a multi-step process, generally characterised by higher rates in water than in physiological serum. The structural effect of silver addition to bismuth-borate glasses is observed from infrared spectroscopic data. The antibacterial activity of the investigated samples was tested on six bacterial media.