The Li(H2O)n(-) and Cs(H2O)n(-) (n = 0-6) clusters were studied using anion photoelectron spectroscopy combined with ab initio calculations. It was found that Li tends to be surrounded by water molecules with no water-water H-bonds being formed in the first hydration shell; while Cs sticks on the surface of water-water H-bonds network. The Li atom in its anionic or neutral state is surrounded by four water molecules through Li-O interactions within the first hydration shell; while the case of Cs is different. For the anionic Cs(H2O)n(-) clusters, two types of structures, namely H-end and O-end structures, were identified, with nearly degenerate energies. For the neutral Cs(H2O)n clusters, only O-end structures exist and the first hydration shell of the Cs atom has four water molecules. The different hydration nature of Li and Cs atoms can be ascribed to the delicate balance between the alkali metal-water interactions and the water-water interactions as well as the effect of excess electron.