Actual lignocellulosic fermentation broth has intrinsic multiphase and multicomponent nature and calls for complex separation systems in both bioethanol recovery and purification [Torres-Ortega, C. E.; Rong, B.-G. Ind. Eng. Chem. Res. 2016, 55, 210]. In this work, we present the synthesis and evaluation of the intensified recovery and purification systems. A three-level methodology intensified the recovery, the purification, and both sections simultaneously. We proposed replacement of flashes by column sections, hybridizing unit operations by reformulating column sections, and relocation of column sections as novel synthesis approaches to formulate hybrid units and divided wall columns. Rigorous simulation in Aspen Plus V8.0 was used to simulate the intensified separation systems. The new intensified alternatives achieved relevant savings, ranging from 17 to 23% in TAC (total annual costs), and ranging from 18 to 28% in TEC (total energy consumption). Moreover, reduction of the number of separation units varied from the original eight units down to three units. Finally, we performed a sensitivity analysis varying the bioethanol concentration in the fermentation broth between the reference case, the intensified system with lowest TAC, and a multieffect distillation column scheme. The intensified system obtained cost savings of 15–20% higher than the multieffect scheme. We concluded that the novel synthesis procedure generated systems that efficiently reduced the energy and capital costs for the bioethanol recovery and purification task.