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The reactive double dividing-wall distillation column (R-DDWDC) can simultaneously integrate and effectively coordinate reaction–separation coupling (RSC) and separation–separation coupling (SSC), thereby offering greater technical advantages and development potential than the conventional reactive distillation column and the reactive single dividing-wall distillation column. However, the application of two dividing walls and the introduction of external recycle flows inevitably lead to multiple candidate configurations of the R-DDWDC, and this significantly adds complexity and computational burden to its synthesis and design. To address the issue, we propose an effective methodology for developing the R-DDWDC, which involves a two-step strategy: the first step is to determine the configuration of external recycle flows by searching for the RSC from non-sharp separation to sharp separation of reaction mixtures, and the second step is to adjust the arrangement of the dividing walls to intensify the SSC. The former serves to provide the greatest flexibility for the inclusion of the SSC, and the latter helps to achieve full coordination with the RSC, thereby allowing the determination of the optimal design with low complexity and computational intensity. The methodology is fundamentally a conceptual design and structural optimization framework that can be implemented using either generic process simulation platforms or custom computational programs. Four representative examples, including the metathesis of 2-pentene; the acetalization of ethanol with butanal; the transesterification of propylene glycol monomethyl ether with methyl acetate; and the esterification of lactic acid with methanol, are selected to assess the derived procedure, and the obtained results confirm its simplicity and efficiency. Because the procedure proposed in this work is independent of the number of components contained in reaction mixtures and their relative volatility rankings, it can be regarded as a general methodology for developing other complicated reactive dividing-wall distillation columns. Full article