The thermoelectric properties of TiN/MgO surface nanostructures have been determined using first-principles calculations based on the nonequilibrium Green's function (NEGF) method. Through structural modification of the surfaces at the atomistic level, we find that the metallic TiN thin-film layer becomes semiconducting with a small bandgap, which enhances the Seebeck coefficient, while the electrical conductivity remains high at room temperature. Hence, a much larger thermoelectric figure of merit is obtained compared with bulk. These findings indicate the possibility of designing thermoelectric devices with surface nanostructures.