Linear α-olefin (LAO) purification from an olefin/paraffin mixture by a simulated moving bed process is regarded as an energy-efficient alternative toward conventional distillation. However, the lack of a systematic study on the thermodynamic and kinetic adsorption behavior of promising adsorbents and the understanding of the gap between the separation performance of adsorbents and technological processes hinders the advance of the olefin/paraffin SMB process. Herein, the selective adsorption of LAOs from a binary liquid-phase 1-octene/n-octane mixture by FAU zeolites was investigated using batch adsorption and fixed bed pulse experiments. Considering the combined effect caused by the thermodynamic and kinetic factors, the octene/octane separation resolution is up to 0.286 with a mass transfer coefficient of 5.8 min −1 under 333 K at a flow rate of 4.00 mL/min. Moreover, based on the nonideal and nonequilibrium SMB mathematical model, the influences of operation parameters (t s , Q rec , Q D , Q E , and Q F ) of the SMB process on the purity and recovery of octene and octane are studied, and 99% purity octene with 99% yield could be obtained under the suitable conditions. This study from the thermodynamic and kinetic adsorption behavior of zeolites toward the ultimate technology process provides guidance for the design of octene/octane adsorbents for practical use.