The effect of increasing sulfate contents on the hydration of white cement was studied with a multi-technique approach. Quantitative X-Ray Diffraction (XRD) revealed that adding more gypsum in the cement resulted in more ettringite formation. Combining isothermal calorimetry, advanced in-situ H-1 nuclear magnetic resonance (NMR) and early scanning electron microscopy (SEM) observations, it was possible to correlate the depletion of the gypsum with a change in C-S-H morphology, from needle-like to agglomerated C-S-H, together with a change in C-S-H gel pore content. Nevertheless, the content of C-S-H interlayer water remained similar and no change in C-S-H pore sizes were observed when increasing the sulfate content. The data allowed to calculate the volume composition of hydrated cement pastes at 3 days of hydration. The more gypsum was added to the cement, the lower was the bulk C-S-H volume due to lower gel pore content and the higher was the content of capillary porosity.