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Large-scale eco-efficient production of polyoxymethylene dimethyl ethers (PODE_n) has garnered wide attention as environmental-friendly diesel additives. Among the various PODE_n research studies, the effect of water on the PODE_n process is one of the most important research fields. In this work, the effects of water content in feedstock on the reboiler duty of the PODE_n process were analyzed by rigorous simulation. To ensure the accuracy of the model, vapor–liquid equilibria (VLE) data of PODE₂-H₂O were measured and the model was regressed by using the experimental data. Furthermore, the production process consisting of raw material preparation section and PODE_n synthesis section was evaluated by comparing it with the various water contents (0, 0.05, 0.10 and 0.15 g/g) in feedstock. We found the reboiler duty in the case of 0.10 g/g water in feedstock was lowest (77.99 MJ/kg), which is even lower than anhydrous case (100.24 MJ/kg). The results suggest that the water can be appropriately allowed in the production, which can reduce the reboiler duty of the PODE_n.