Abstract: By applying the method developed in part (Ⅰ) of this paper series for the formulation and solution of the problems of synthesis of thermally coupled complex distillation system, three example problems for five-component mixtures separation were solved to illustrate the implementation and effectiveness of the proposed procedure.In each case, six sub-schemes were solved respectively.The optimized parametes and economic benefits of different optima scenarios were analyzed and compared.Some preliminary insights into the rules for synthesis and design of multi-component thermally coupled complex distillation systems were presented as well.