The knowledge of the chromate binding mechanisms is essential for the prediction of the long-term leachability of cement-based solidified waste containing increased chromate concentrations because of its toxicity and high mobility. In this paper pore water concentrations from OPC doped with varying CaCrO4 concentrations (0.01–0.8 mol/kg), equilibrated for 28 days were reported. It could be shown that the cementitious matrix can bind chromate concentrations up to 0.1 mol/kg and that the chromate solubility limiting phase was CrO4-ettringite, while chromate containing AFm (monochromate) was unstable. Comparison with thermodynamic modelling indicated that at lower chromate dosages chromate was mainly bound by CrO4-ettringite while at very high dosages also a mixed CaCrO4–CaSO4·2H2O phase precipitated. Additional experiments indicated a solubility product of 10−3.66 for CaCrO4 and verified the solid solution formation with CaSO4·2H2O. Leaching tests indicated a strong chromate binding mainly in the pH range 10.5–13.5, while at pH < 10 very little chromate was bound as ettringite, monocarbonate and C–S–H phases were destabilized. Generally the thermodynamic modeling underestimated chromate uptake indicating that an additional chromate binding possibly on C–S–H or on mixed chromate–carbonate–hydroxide AFm phases.