To mitigate autogenous shrinkage in cementitious materials and simultaneously preserve the material’s mechanical performance, superabsorbent polymers and nanosilica are included in the mixture design. The use of the specific additives influences both the hydration process and the hardened microstructure, while autogenous healing of cracks can be stimulated. These three stages are monitored by means of non-destructive testing, showing the sensitivity of elastic waves to the occurring phenomena. Whereas the action of the superabsorbent polymers was evidenced by acoustic emission, the use of ultrasound revealed the differences in the developed microstructure and the self-healing of cracks by a comparison with more commonly performed mechanical tests. The ability of NDT to determine these various features renders it a promising measuring method for future characterization of innovative cementitious materials.