The production of butadiene from bioethanol as a non-oil route has become a new research focus. Due to the incomplete conversion of ethanol and acetaldehyde in a single pass it is necessary to recycle the unreacted raw material. On the basis of economic optimization, a new acetaldehyde and ethanol recovery process with optimized operation conditions was developed. The purity of ethanol and acetaldehyde returned to the reactor can be guaranteed. The energy bottleneck of the process was identified by exergy analysis and improved by the proposed thermal integration. Sensitivity analysis was carried out to seek proper parameters for each operation unit. Total utilities cost, energy consumption, and exergy loss in the thermal integrated scheme could be significantly reduced.