The unique properties of radon as a noble gas are used for monitoring cement hydration and microstructural transformations in cementitious system. It is found that the radon concentration curve for hydrating cement paste enclosed in the chamber increases from zero (more accurately - background) concentrations, similar to unhydrated cement. However, radon concentrations developed within 3 days in the test chamber containing cement paste were approximately 20 times higher than those of unhydrated cement. This fact proves the importance of microstructural transformations taking place in the process of cement hydration, in comparison with cement grain, which is a time-stable material. It is concluded that monitoring cement hydration by means of radon exhalation method makes it possible to distinguish between three main stages, which are readily seen in the time dependence of radon concentration: stage I (dormant period), stage II (setting and intensive microstructural transformations) and stage III (densification of the structure and drying). The information presented improves our understanding of the main physical mechanisms resulting in the characteristic behavior of radon exhalation in the course of cement hydration. The maximum value of radon exhalation rate observed, when cement sets, can reach 0.6 mBq kg(-1) s(-1) and sometimes exceeds 1.0 mBq kg(-1) s(-1). These values exceed significantly to those known before for cementitious materials. At the same time, the minimum ventilation rate accepted in the design practice (0.5 h(-1)), guarantees that the concentrations in most of the cases will not exceed the action level and that they are not of any radiological concern for construction workers employed in concreting in closed spaces.