Superplasticizers are widely used in concrete processing to increase the rheological properties of hardening pastes. In this study, different techniques (rheology, adsorption, atomic force microscopy—AFM, and ζ-potential) are used to characterize the impact of polycarboxylate-ether based superplasticizer (PCE) on particle suspensions. Results obtained with two cements and two inert powders (MgO and calcite) show that superplasticizer efficiency is strongly influenced by polymer architecture and by the ionic species present in solution. Additionally, experiments performed with AFM and ζ-potential contributed to characterize dispersion forces exerted by superplasticizers at the solid–liquid interface. The application of plateau AFM-tips coated with platinum reveals that dispersion forces depends on the presence of ions in solution, and that multilayer formation occurs with certain superplasticizer types. A further conclusion includes the idea that the PCE has a lubricating effect between adjacent particles and PCE increases surface wettability.