Because of their importance in both the geosciences and the glass-making industry, alkali aluminosilicate melts have been the focal point of many past studies, but despite progress many problems remain unresolved, such as the complex behaviour of the thermodynamic properties of aluminium-rich alkali silicate melts. This paper presents a study of Na2O–Al2O3–SiO2 glasses and melts, containing 75mol% SiO2 and different Al/(Al+Na) ratios. Their structure has been investigated by using Raman spectroscopy, as well as, 23Na, 27Al and 29Si 1D MAS NMR spectroscopy. Results confirm the role change of Na+ cations from network modifier to charge compensator in the presence of Al3+ ions. In addition, polymerization increases with increase of the Al/(Al+Na) ratio. These structural changes explain the observed variations in the viscosity of these melts. The viscosity data in turn allow us to calculate the configurational entropy of melts at the glass transition temperature [the Sconf(Tg)]. The variations of the Sconf(Tg) are strongly nonlinear, with sharp increases and decreases depending on the Al/(Al+Na) ratio. More importantly, a strong increase of the Sconf(Tg) is observed when a few Al2O3 is added to sodium silicate melt. A strong decrease is observed after crossing the tectosilicate join, when Al/(Al+Na)>0.5 and when Al3+ ions are present in fivefold coordination, Al[5], in the glass. Furthermore, in situ27Al NMR spectra of the peraluminous melt show a clear increase of the Al[5] concentration with increasing temperature. When considered in combination with melt fragility and heat capacity, our data demonstrate that Al[5] is clearly a transient unit at high temperature in highly polymerized tectosilicate and peraluminous melts. However, when present in glasses, Al[5] increases the stability of the aluminosilicate network, hence the Tg of glasses. This could be explained by the ability of Al[5] to carry threefold coordinated oxygen atoms in its first coordination shell, as observed in minerals. Localisation of threefold coordinated oxygen atoms on Al[5] implies an increase of the medium-range order in the glass, an hypothesis that is in agreement with the low Sconf(Tg) of peraluminous glasses.