The fluid catalytic cracking (FCC) naphtha critical component‐oriented separation process is an efficient method to produce ultra‐low‐sulfur (<10 μg/g) gasoline with minimal loss of octane number (<1 RON). However, the product quality is highly dependent on the structure of the components of FCC naphtha. Aromatics and thiophene sulfides without a methyl side chain favor the separation of olefin. The major impulse of olefin separation is the solvent‐induced dipole of aromatics or thiophene sulfides, leading to a “Plane‐to‐Plane” combination between the solvent and aromatics or thiophene sulfides, accompanied by a steric hindrance due to their side chains. This condition resulted in 2–3 times greater θ of benzene and thiophene compared with that of toluene and 3‐methylthiophene. In addition, an improved non‐random two‐liquid model was proposed based on the above results, and a simulation method for FCC naphtha solvent extraction process was established. The calculation results accorded well with industry data.