The hydration of tricalcium aluminate (C3A) has a significant effect on the effectiveness of cement-based systems. In addition, the carbonation of hydration products of C3A is particularly important in respect of durability performance. The present work investigates the hydration and carbonation reactions of C3A and the changes induced by the presence of the heavy metal ions such as Zn2+, Pb2+, Cu2+ and Cr3+ by X-ray diffractometry (XRD). During hydration of C3A, gehlenite hydrate, hydrogarnet, calcium monoaluminate (C4AHx) and calcium carboaluminate were detected in C3A pastes except the Zn2+doped paste, where hydrogarnet did not form. The examinations revealed that heavy metals coexisted with gehlenite hydrate, calcium monoaluminate (C4AHx) and calcium carboaluminate, inhibiting the formation of hydrogarnet. Hydrating C3A was liable to be carbonated on exposure to air and carbon dioxide, especially in the presence of heavy metals, resulting in the formation of carboaluminate and/or calcium carbonate. The presence of heavy metals in-fluenced the polymorphism of calcium carbonate,ndicating that heavy metals could co-precipitate with calcium to form a carbonate solid solution.