The environmental footprint of concrete is largely influenced by the binder. It is therefore of high interest to investigate the potential reuse of the binder retrieved by modern separation techniques. However, studies found that the recycled cement fraction (RCF) still contained a certain amount of siliceous concrete aggregates, which forms an obstacle in the upcycling of RCF. In this study, the potential of electrostatic separation as a method to separate cementitious binder (hydrated and unhydrated) and sand (silica) is evaluated. Different cementitious powders and silica (sand) were prepared, resulting in a total of 9 powders and 8 mixtures. The mixtures consisted of a combination of silica and one of the cementitious powders (50/50 wt%) with a particle size of the components <125 μm. The potential of the studied technique was evaluated through charging measurements and x-ray fluorescence (XRF). Silica was assumed to contain no CaO and the detected CaO was therefore assigned to the cementitious powders. Results showed that silica and silica-rich fly ash (FA) particles became negatively charged, blast furnace slag (BFS) particles remained largely charge neutral and all other cementitious particles obtained a positive charge. Through electrostatic separation an enrichment of the cementitious binder fraction for all mixtures was obtained at the negative electrode. FA-Silica achieved the highest enrichment (89.9%), CEM III/B-Silica the lowest (4.7%) and the hydrates were enriched ranging from 28.0 to 31.8%.