In this study we investigate the influence of post-growth annealing on different Co2Cr0.6Fe0.4Al samples. We find strong changes in the geometric surface structure as well as in the element specific concentrations during the annealing process. These irreversible changes go in hand with characteristic changes in the electron spin polarization (ESP) at the surface: as observed in Cinchetti et al (2007 J. Phys. D: Appl. Phys. 40 1544), the iron buffered sample shows the largest spin polarization at the Fermi level. The latter remains positive as a consequence of the reduced density of states for the minority carriers due to the predicted minority gap, which can be clearly seen for all samples above the proposed minimum annealing temperature of 400 degrees C. Above this temperature we observe a characteristic dip in the ESP as a sign of increasing structure quality. It appears at 0.6 eV binding energy and is consistent with a peak in the minority electron density of states seen in both experiment and theory.