The structure and dissolution behaviour of Na 2 O•CaO•(15-x)Al 2 O 3 •xB 2 O 3 •SiO 2 and Na 2 O•MgO•(15x)Al 2 O 3 •xB 2 O 3 •SiO 2 glasses, relevant to compositions of UK nuclear waste glass, have been investigated using nuclear magnetic resonance (NMR) spectroscopy and static dissolution experiments using the PCT protocol. Structural data from 11 B, 27 Al and 29 Si NMR analyses show that increasing the Increasing the [B 2 O 3 ]/([Al 2 O 3 ]+[B 2 O 3 ]) ratio of the alkali-alkaline-earth aluminoborosilicate glasses led to an overall decrease in the proportion of non-silicate tetrahedral species (IV Al + IV B) and a decrease in Si-OX bonds (X = B, Al). The Mg-containing glasses exhibited lower IV B fractions than their Ca-containing counterparts, which is thought to be due to the presence of IV Mg tetrahedra in the network. The measured corrosion rates were similar for both Ca and Mgcontaining glasses although unexpectedly some Ca-containing glasses exhibited higher corrosion losses than the Mg-containing ones for time periods up to 112 d. However, there was evidence of a greater tendency to rate resumption in the Mg containing than the Ca containing ones. Alteration products were found to contain Ca, Si and Al with the Ca containing glasses and Ca, Mg, Si and Al with the Mg containing glasses; Na was not detected in the alteration products although its presence cannot be ruled out based on the data obtained.