A new acetic acid separation method was developed through a successful combination of cloud point extraction and complex extraction technology (CPE-SE), where an acetic acid complex compound formed and was solubilized in a surfactant micelle solution, instead of an organic solvent, and then concentrated into one phase by a phase separation process of the CPE technology. Since no organic solvent diluents were used, the new process was environmentally friendly and with a lower cost; meanwhile, the high selectivity of the complex extraction based on chemical complexation and high efficiency of CPE were also inherited as advantages over conventional solvent extraction process. In consideration of the compatibility and the related CPE characteristics, tributyl phosphate and PEG/PPG-18/18 Dimethicone were selected as complexing agent and surfactant of the CPE-SE system, respectively, and the extraction system was optimized by studying the effect of the main process parameters, including surfactant and complexing agent concentration, temperatures for the stirring and incubation steps, on the recovery and the distribution coefficient. A relative high recovery of 71.4% and a distribution coefficient of 1.4 were achieved simultaneously with the optimized process in the treatment of 0.1M acetic acid solution. Based on its competitive extractability, high efficiency, low-cost, and environment friendlyness, the CPE-SE process was expected to be a potential separation method for a dilute acetic acid solution.