The aim of this study was to prepare and to characterize the structure of Al2O3-3YSZ composites with 5% TiO2 addition as well as the surface modification upon treatments with SnF2 and NaBF4, respectively. SEM micrographs showed the controlled densification of the composites as an effect of 3YSZ and TiO2 addition to alumina matrix. By FTIR and XRD, the characteristics of Al-O and Zr-O vibrations, respectively, the diffractions lines related to α-corundum and zirconia in tetragonal phase were discussed. Qualitative and quantitative results obtained by XPS and ATR FTIR demonstrated that the proposed materials are more sensitive to SnF2 than to NaBF 4 treatment. © 2013 The American Ceramic Society.