A new principle for controlling the deformation behavior of composite materials is presented using cementing systems as an example. The approach is based on the creation of a “core-shell” architecture, where the expanding additive is encapsulated in a two-layer polymer shell, providing signal-dependent activation. It was established that dissolution of the inner layer is initiated upon reaching a critical concentration of calcium ions in the intergranular space, which deterministically links the onset of expansion to a specific stage of hydration. This ensures synchronization of the expansion process with the phase of active structure formation, when the elastic modulus of the matrix exceeds 18 MPa, and leads to the transformation of expansion energy into effective compressive stresses. It has been quantitatively confirmed that the application of this approach provides a sevenfold increase in the expansion efficiency criterion, almost complete (95%) compensation of shrinkage deformations, and an increase in adhesive strength by 94%. The developed concept opens up prospects for the design of a new class of smart materials with a deterministic response for practically significant applications.