Employing high resolution photoemission spectroscopy, we investigate the temperature evolution of the electronic structure of CaFe2As2, which is a parent compound of high temperature superconductors—CaFe2As2 exhibits superconductivity under pressure as well as doping of charge carriers. Photoemission results of CaFe2As2 in this study reveal a gradual shift of an energy band, α away from the chemical potential with decreasing temperature in addition to the spin density wave (SDW) transition induced Fermi surface reconstruction across SDW transition temperature. The corresponding hole pocket eventually disappears at lower temperatures, while the hole Fermi surface of the β band possessing finite p orbital character survives till the lowest temperature studied. These results, thus, reveal signature of complex charge redistribution among various energy bands as a function of temperature.