A lower generation hyperbranched molecular skeleton R-12-1.0G was synthesized with methanol as solvent by means of Michael addition and amidation condensation reaction with C-12 fatty amine, acrylate, and ethylenediamine as raw materials. The structure was characterized by IR and H-1 NMR spectrum. Two lower generation hyperbranched polyethers were further synthesized by means of a skeleton as raw materials through addition reaction with epoxyethane and epoxypropare, respectively. The surface tension, cloud point, and HLB value of the hyperbranched polyethers were determined systematically. On this basis, the demulsification of two hyperbranched polyethers for simulated emulsion was studied in this paper. The results showed that two hyperbranched polyethers are typical surfactants, and they show different demulsification for the simulated emulsion. The structure of polyethers can influence the demulsification performance, and the main factor is the molecular block structure. The demulsification mechanism of two hyperbranched polyethers was studied using the single-droplet protocol, and the dynamic data of drainage time, half life time, and rupture rate constant obtained are consistent with the demulsification law of the hyperbranched polyethers. This study may be helpful in accounting for the demulsification mechanism and for developing effective demulsifiers with new structure.