Ceramic materials like zirconia and alumina are becoming more and more important in the biomedical area. With the development of 3D printing techniques, as vat photopolymerization (VPP), the design and manufacturing of complex geometries for Bone Tissue Engineering (BTE) scaffolds became possible. Multilayer geometries have been proposed to increase toughness, slow crack propagation and improve reliability. The study of the residual stresses in 3D layered geometries is difficult to be predicted by analytical models and few experimental tests have been conducted to analyse the stress profile. Employing the X-ray Synchrotron Diffraction, and particularly the Laue microdiffraction, it’s possible to evaluate the superficial stress profile for a depth up to hundreds of micrometres. The experimentally obtained stress data can be used to validate numerical models which predicts the residual stresses in complex geometries and assess the overall apparent toughness of layered 3D BTE scaffolds.