There exists limited information regarding the effect of temperature on the structure and solubility of calcium aluminosilicate hydrate (C-A-S-H). Here, calcium (alumino)silicate hydrate (C-(A-)S-H) is synthesised at Ca/Si = 1, Al/Si ≤ 0.15 and equilibrated at 7-80°C. These systems increase in phase-purity, long-range order, and degree of polymerisation of C-(A-)S-H chains at higher temperatures; the most highly polymerised, crystalline and cross-linked C-(A-)S-H product is formed at Al/Si=0.1 and 80°C. Solubility products for C-(A-)S-H were calculated via determination of the solid-phase compositions and measurements of the concentrations of dissolved species in contact with the solid products, and show that the solubilities of C-(A-)S-H change slightly, within the experimental uncertainty, as a function of Al/Si ratio and temperature between 7°C and 80°C. These results are important in the development of thermodynamic models for C-(A-)S-H to enable accurate thermodynamic modelling of cement-based materials.