Ti K -edge x-ray absorption near-edge spectroscopy (XANES) and Raman scattering were used to study the solid solution effects on the structural and vibrational properties of Pb _1-x Ba _x Zr _0.65 Ti _0.35 O ₃ with 0.0≪x≪0.40 . Compared with x-ray diffraction techniques, which indicates that the average crystal symmetry changes with the substitution of Pb by Ba ions or with temperature variations for samples with x=0.00 , 0.10, and 0.20, local structural probes such as XANES and Raman scattering results demonstrate that at local level, the symmetry changes are much less prominent. Theoretical XANES spectra calculation corroborate with the interpretation of the XANES experimental data.