Ceramic monolithic and multilayered composites were produced by stacking water based green ceramic cast tapes. Two different mixtures of composites within the Al2O3/YTZP, system were investigated. The difference in the coefficient of thermal expansion (CTE) between the composites fabricated, resulted in the development of residual stresses when the same compositions were combined in a multilayered structure. The magnitude and the distribution of these residual stresses were assessed by the piezo-spectroscopic technique. The stress within the layers varied with a parabolic trend, with the highest values at the interfaces and a reduction toward the centre of the layers. The influence of symmetry of the multilayered laminate on the magnitude and distribution of the residual stresses within the structure are discussed.