We investigate the role of ligand states in the electronic properties of CaFe2As2 using high-resolution hard x-ray photoemission spectroscopy (HAXPES) at different sample temperatures. Experimental results indicate that the binding energy of Ca is close to that for 2+ charge state of Ca atoms and the other constituent elements, Fe and As possess electronic configuration close to that in elemental systems. No difference is observed in the As 3p core level spectra with the change of emission angle and/or the change in sample temperature. This is surprising as the Ca atoms at the cleaved sample surface reorganizes itself to form linear structures which is expected to influence Ca-As hybridization leading to significant difference in surface and bulk electronic structures. Moreover, CaFe2As2 undergoes structural and magnetic phase transition at 170 K, and strong Fe-As hybridization provides pathways for electron dynamics. Clearly, further studies are required to resolve these puzzling observations.