In this work, a process consisting of Mechanical Vapor Recompression (MVR) heat pump distillation coupled with Organic Rankine Cycle (ORC) was proposed to separate the benzene-toluene mixture. Aspen Plus (version 7.3) was used to study the steady state simulations of the process. An optimized ORC system was applied to recover waste heat from the MVR heat pump system. In addition, the optimized parameters of ORC waste-heat power generation process were obtained based upon the net power output and cycle's thermal efficiency. All other parameters, including operating and equipment parameters for the whole process were based upon the total annual cost (TAC). The results showed that the MVR heat pump distillation coupled with ORC process was more competitive than the conventional distillation process. Additionally, the proposed process was found to be more economical than the MVR heat pump distillation process. (C) 2017 Elsevier Ltd. All rights reserved.