Heat-operated absorption refrigeration, using the working pair water-Lithium bromide (LiBr), is attracting lots of attentions from researchers, for a broad market prospect in energy saving. Improving the absorption speed is thought to be important in advancing system efficiency and reducing the exchange area in LiBr absorption refrigeration system. Adding a little amount of surfactant additives such as 2-ethyl-1-hexanol into LiBr solution can enhance the heat and mass transfer process greatly. Due to its great application value, numerous studies have been carried out to understand the mechanism of absorption enhancement by surfactant additives. Molecular dynamics simulation is adopted to study the impact of the types, the number of alcohols and the concentrations of LiBr solution on microscopic structure of the liquid-vapour interface of the mixture of alcohols and electrolyte solution. The computed results reveal that n-alcohol molecules tend to adsorb at the interface with the preferred orientation, meanwhile, the tendency of this kind of preferred orientation becomes distinct with the increase of the amount of n-alcohol. The interface thickness increases with the number of n-alcohols or the length of hydrocarbon chains. The dynamic process of water vapour absorption into aqueous electrolyte solution with or without alcohol additive surfactants is explored by molecular dynamics simulation under non equilibrium conditions. The simulation results suggest that in comparison to the lithium bromide aqueous solution without surfactants, the electrolyte aqueous solution with surfactants can absorb more water molecules distinctly, which conforms to the relevant experimental tendency.