This article presents a simulated annealing-based approach to the optimal synthesis of distillation column considering intermediate heat exchangers arrangements. The number of intermediate condensers and/or intermediate reboilers, the placement locations, the operating pressure of column, and the heat duties of intermediate heat exchangers are treated as optimization variables. A novel coding procedure making use of an integer number series is proposed to represent and manipulate the structure of system and a stage-to-stage method is used for column design and cost calculation. With the representation procedure, the synthesis problem is formulated as a mixed integer nonlinear programming (MINLP) problem, which can then be solved with an improved simulated annealing algorithm. Two examples are illustrated to show the effectiveness of the suggested approach.