Multiple layers of water on Au (111) surface are studied using first principle computations within the framework of Density Functional Theory. Gold surface coverage of one (1L), two (2L) and three (3L) water layers were analyzed. The ratio of Au surface atoms to water molecules in 1L, 2L, and 3L corresponds to 1:1, 1:2, and 1 :3, respectively. The first two water layers are unique in energy and structure as compared to ice like layers and are only stable at the interface. Thus the interfacial region was defined by the region created by the first two water layers. The third water layer adopts a structure that is close to that of an ice water layer in geometry and energy. The dielectric response of bulk water is recovered at the 3rd water layer signifying the transition from interfacial water to bulk water which occurs at a surface coverage that is greater than (2L). The first water layer is defined as the water bilayer which is adjacent to the Au (111) hexagonal surface. This bilayer structure changes significantly with the addition of the second water layer whereas additional layers added thereafter generate insignificant changes. The bilayer structure and hence the dielectric response of the layer is a function of the presence of surrounding water layers. The rapid decrease in the work function of gold with an increase in the number of water layers becomes less pronounced as more layers are added and asymptotically attains a constant value once the bulk properties of water are reproduced. The calculated decrease of work function for a surface coverage greater than 2L matches the experimental results. (C) 2015 Elsevier B.V. All rights reserved.