AbstractObjective  To characterize the hydration products of white mineral trioxide aggregate (MTA).Methodology  Mineral trioxide aggregate, white Portland cement and bismuth oxide were evaluated using X‐ray diffraction (XRD) analysis and Rietveld XRD. The cements were tested un‐hydrated and after hydration and curing for 30 days at 37 °C. Analysis of hydrated cement leachate was performed weekly for five consecutive weeks from mixing using inductively coupled plasma atomic emission spectroscopy after which the cements were viewed under the scanning electron microscope to evaluate the cement microstructure. Quantitative energy dispersive analysis with X‐ray was performed and atomic ratios were plotted.Results  Both Portland cement and MTA produced calcium silicate hydrate (C‐S‐H) and calcium hydroxide (CH) on hydration. The tricalcium aluminate levels were low for MTA which resulted in reduced production of ettringite and monosulphate. On hydration the bismuth level in the hydrated MTA decreased; bismuth oxide replaced the silica in the C‐S‐H and was leached out once the C‐S‐H decomposed with time. Both MTA and Portland cement released a high amount of calcium ions which decreased in amount over the 5‐week period.Conclusions  The hydration mechanism of MTA is different to that of Portland cement. In MTA the bismuth oxide is bound to the C‐S‐H and is leached out from the cement with time as the C‐S‐H decomposes. MTA produces a high proportion of calcium ions from CH a by‐product of hydration and also by decomposition of C‐S‐H. The release of calcium ions reduces with time.