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BACKGROUND: C8 α‐olefins are regarded as top value‐added compounds from Fischer–Tropsch (F−T) products. However, the separation of purified C8 α‐olefins has proven to be a daunting challenge owing to their relative volatility. As the traditional methods for C8 α‐olefins purification are energy‐ and capital cost‐intensive, an efficient method for the separation of n‐hydrocarbons and iso‐hydrocarbons will provide a valuable and more sustainable alternative to address these challenges. RESULTS: In the urea‐adduction method, the purity of 1‐octene was increased from 96.02 to 98.04 wt%, and the yield was 93.62 %, which broke the limitation of traditional distillation on the purification of 1‐octene. By combining the urea‐adduction method and distillation, a promising and energy‐efficient integrated separation process was proposed. First, it recovers C8n‐hydrocarbons through adduction reactions. Second, 1‐octene and n‐octane are separated with integrated distillation technology. The results indicated that this process can be utilized to recover 1‐octene from the C8 fraction of F–T synthetic products with a recovery yield of 93.6 % and an increase in purity from 65.6 to 98.7 wt%. As shown in Fig. 6(b), process modeling demonstrates that it trims energy consumption to 50.1% and total TAC to 55.1% in comparison with the traditional separation process. CONCLUSION: It was found that the integrated process can produce high‐purity 1‐octene, indicating that the integration process demonstrates clear potential advantages, such as reducing energy consumption and increasing economic value. This approach can be adopted on an industrial scale. © 2022 Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]