Aiming at achieving the high-purity recovery of ethanol (EtOH) and tert-butanol (TBA) from industrial waste with low carbon emission, the processes intensified by hybrid reactive distillation combined with pressure-swing distillation (PSD) and extractive distillation (ED) are proposed in this work. The optimum procedure of the sequential iterative method is applied to select an optimal pressure for these hybrid reactive distillation processes. From the economic and environmental impact perspective, the results indicated that the reactive-extractive-/pressure-swing hybrid distillation has significant economic and environmental advantages. The REPDC-REPC (reactive-extractive-/pressure-swing hybrid distillation) process is the most potential and competitive, saving 56.47% TAC and reducing 69.23% CO2 emissions, and has 67.51% thermodynamic efficiency, minor exergy destruction, and most enormous total exergy efficiency. Meanwhile, the work also demonstrates that the operating pressure of the column plays an important role, which positively affects the energy saving of the recovery process.