a b s t r a c tThe microstructure of calcium-silicate-hydrate (CÀSÀH) gel, a major hydrated phase of Ordinary Portland Cement, with and without polycarboxylic ether (PCE) additives is investigated by combined analyses of small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) data. The results show that these comb-shaped polymers tend to increase the size of the disk-like globules but have little influence on the thickness of the water and calcium silicate layers within the globules. As a result, the fractal packing of the globules becomes more open in the range of a few hundred nanometers, in the sense that the mass fractal dimension diminishes, since the PCE adsorption on the globules increases the repulsive force between and polydispersity of the CÀSÀH units. Moreover, scanning electron microscope (SEM) study of the synthesized CÀSÀH gels in the micrometer range shows that the PCEs depress the formation of fibrils while enhancing the foil-like morphology.