Despite water being a ubiquitous substance, it is surprising that some basic questions are still debated. Here using a combination of experimental (cryogenic STM) and theoretical (first-principle electronic structures and molecular dynamics) methods, we systematically studied the unusual structure and dynamics of water molecules on NaCl surface. More interestingly, for the first time, we observe the full quantum effect and magic number hydrates in water system. These results shed light on our understanding of water at atomic scale.