Calorimetry was applied to follow the hydration of special cement mixtures exhibiting expansion or shrinkage compensation. The standard, common cements show generally less or more visible shrinkage on setting and hardening but mixed with and expansive agent, usually of aluminate and sulfate nature, they can exhibit the increase of volume. The calcium aluminate cement CAC 40 was ground together with special sulfate–lime sinter to produce an expansive additive to Portland cement (CEM I 42.5R). The expansive additive in the environment of hydrating cement transforms into ettringite at “right time” to give expansion before the final setting and hardening takes place. In the experiments the proportions of components of expansive mixture and basic cement were variable. The rate of hydration versus time for common cements is commonly known and reflects the moderate setting and early hardening during the first days after mixing with water (two peaks and the induction period between them). The aim of measurements presented in this study was to show the course of heat evolution curve and the heat evolved values, equivalent to the acceleration/retardation of hydration, in case of the paste with the expansive mixture, as well as the pastes produced from Portland cement and the components of expansive additives added in variable proportions. It was possible to see how the calorimetric curve and consequently the hydration process itself declines from the controlled setting/hardening. These measurements were supplied by the examples of phase composition studies by XRD.