An external de voltage was applied to cured cement pastes to simulate their natural degradation over time; i.e. migration of ions and dissolution of solid phases. The presence of crystalline phases before and after applying a voltage was quantified by powder diffraction using synchrotron X-ray radiation. The results were refined by the Rietveld method. The specimens were also analysed by mercury intrusion porosimetry. Results indicated that a portion of the crystalline phases dissolved and later precipitated as amorphous phases in smaller pores. This accelerated treatment led to the formation of a larger proportion of amorphous phases in the specimens studied.