Methacrylate ester as well as allylether based polycarboxylates (PCEs) were synthesized to plasticize pastes of cement and silica fume having a water/cement ratio of 0.22. Methacrylate ester copolymers were found to disperse cement well, whereas allylether copolymers are more effective with silica fume. Mechanistic investigations revealed that in cement pore solution, the surface charge of silica fume becomes positive by adsorption of Ca²⁺ onto negatively charged silanolate groups present on the silica surface. This way, polycarboxylate copolymers adsorb to and disperse silica fume grains. Thus, mixtures of both copolymers were tested in cement-silica fume pastes. These blends provide significantly better dispersion than using only one polymer. Apparently, the surfaces of hydrating cement (here mainly ettringite) and silica fume are quite different with respect to their chemical composition. Therefore, PCEs with different molecular architectures are required to provide maximum coordination with calcium atoms present on these surfaces.