The interaction of CO2-rich water with olivine was studied using geochemical reaction modelling in order to gain insight into the effects of temperature, acid supply (CO2) and extent of reaction on the secondary mineralogy, water chemistry and mass transfer. Olivine (Fo93) was dissolved at 150 and 250ºC and pCO2 of 2 and 20 bar in a closed system and an open system with secondary minerals allowed to precipitate. The progressive water–rock interaction resulted in increased solution pH, with gradual carbonate formation starting at pH 5 and various Mg-OH and Mg-Si minerals becoming dominant at pH>8. The major factor determining olivine alteration is the pH of the water. In turn, the pH value is determined by acid supply, reaction progress and temperature.