Process intensification is aimed to integrate different processes in design to reduce energy consumption and capital investment, as well as to achieve environmental and safety benefits. Reactive distillation and thermally coupled distillation are examples of such process intensification. In this study, the performance of thermally coupled reactive distillation, a technology combining reactive distillation and thermally coupled distillation, is investigated for ideal quaternary reaction systems with different rankings of relative volatility. Possible configurations of thermally coupled reactive distillation are designed for systems of types I-R, IIR, and IIR with the excess design and type Hp with the stoichiometric design. Reactive distillation with thermal coupling is demonstrated to provide better energy efficiency than conventional reactive distillation. The remixing phenomenon associated with thermodynamic inefficiency in conventional distillation sequences can be reduced or eliminated by implementing thermal coupling between columns.