In an IR spectroscopic study, we have investigated the ligand and solvation shells of the giant Pd561Phen60(OAc)180 cluster, where Phen = 1,10-phenanthroline and OAc- are acetate anions, in the solid state and in colloid solutions of acetic acid. Based on the data obtained, we revised the previous idealized model of the cluster which concerns the palladium nucleus-liquid interface. In the solid, the ligand shell of the cluster consists of coordinated Phen and OAc- ligands with a very low content of noncoordinated outer-spheric acetate anions. In acetic acid colloid solutions, interaction of HOAc molecules with coordinated OAc- anions results in quantitative removal of the latter from the ligand shell, forming (OAcċnHOAc)-ċkHOAc complex anions with n≈8 or 9 and k≈20. The anions comprise the outer-spheric solvation shell of the cluster, while the coordination shell contains only phenanthroline ligands.