Positron annihilation spectroscopy (PAS), indentation, nanoindentation experiments and scanning electron microscopy (SEM) observations were performed on Al2O3–ZrO2 laminates samples to assess the effect of residual stresses on their mechanical and microstructural properties. Layered samples were implemented by slip-casting, constituted by two thin Al2O3 external layers and an intermediate thick one, consisting of a mixture of Al2O3 and monoclinic ZrO2 in the range 0–30 vol.%. In these systems residual tensile stresses fields were generated inside the external layers during cooling from the sintering temperature, by the expansion of the adjacent ZrO2-containing layer. SEM observations showed the microstructural effects due to the level of tension related to the zirconia content. A correlation between the PAS parameters and the microstructural changes caused by the presence of residual stresses was found. Nanoindentation measurements were used to trace the sign and magnitude of the residual stress gradient across the interface between the layers.