This paper investigates the effect of KOH and NaOH on C-S-H structure and solubility. Both KOH and NaOH have a similar effect, they increase pH values and silicon concentrations, and decrease calcium concentrations. At higher alkali hydroxide concentrations, more portlandite precipitates, while amorphous silica dissolves. This increases the Ca/SiC-S-H at low Ca/Si-target but lowers the maximum Ca/Si(C-S-H )from 1.5 to 1.2 in 1 M KOH/NaOH. The amount of alkalis bound in C-S-H increases with increasing alkali hydroxide concentrations and is higher at low Ca/SiC-S-H. KOH/NaOH lead to a structural rearrangement in C-S-H, increasing the interlayer distance, number of layers stacked in c direction and shortening the silica chains. The mean chain lengths (MCL) estimated from FTIR and Raman spectroscopy agree well with the trends from Si-29 NMR. Comparison with the independently developed CASH+ thermodynamic model showed a good agreement between the observed and modelled changes, including the shortening of the MCL.