The degradation of the surface chemistry on perovskite (ABO3) oxides is a critical issue for their performance in energy conversion systems such as solid oxide fuel/electrolysis cells and in splitting of H2O and CO2 to produce fuels. This degradation is typically in the form of segregation and phase separation of dopant cations from the A-site, driven by elastic and electrostatic energy minimization and kinetic demixing. In this study, deposition of Ti at the surface was found to hinder the dopant segregation and the corresponding electrochemical degradation on a promising SOFC cathode material, La(0.8)Sr(0.2)CoO3 (LSC). The surface of the LSC films was modified by Ti (denoted as LSC-T) deposited from a TiCl4 solution. The LSC and LSC-T thin films were investigated by electrochemical impedance spectroscopy, nano-probe Auger electron spectroscopy, and X-ray photoelectron spectroscopy (XPS), upon annealing at 420-530 °C in air up to about 90 hours. The oxygen exchange coefficient, k(q), on LSC-T cathodes was found to be up to 8 times higher than that on LSC cathodes at 530 °C and retained its stability. Sr-rich insulating particles formed at the surface of the annealed LSC and LSC-T films, but with significantly less coverage of such particles on the LSC-T. From this result, it appears that modification of the LSC surface with Ti reduces the segregation of the blocking Sr-rich particles at the surface, and a larger area on LSC surface (with a higher Sr doping level in the lattice) is available for the oxygen reduction reaction. The stabilization of the LSC surface through Ti-deposition can open a new route for designing surface modifications on perovskite oxide electrodes for high temperature electro- and thermo-chemical applications.