This paper presents a novel distillation and separation process: Pressure Swing Thermally Coupled Distillation, and investigates the performance of the process by separating 24 different kinds of binary hydrocarbon mixtures with different boiling point differences by this process, and calculates their cost-saving efficiency in comparison with conventional distillation column, respectively. This work focuses on the comparison of cost-saving efficiency, and adopts the comparison methods of standard coal equivalent and total annul cost calculation. Based on the comparison results, this process is optimized and confirmed that it is more cost-saving than conventional distillation and even heat-pump distillation for the separation of binary systems; therefore, this process will increase distillation efficiency greatly and save much energy for all the world, and thus it is worth considering the practical application and this paper will supply valuable guidelines and simulation calculation basis for industrial application.