Abstract The present work is focused on the comprehensive kinetic modeling of the Fischer–Tropsch synthesis (FTS) over a [email protected]/γ-Al2O3 core–shell structure catalyst in a fixed bed reactor. The elementary reactions for FTS are derived via Langmuir–Hinshelwood–Hougen–Watson (LHHW) method. The kinetic expressions for n-paraffin and olefin formation are developed on the basis of combining alkyl and alkenyl mechanisms without taking into account the readsorption and secondary reactions of olefins. To optimize the parameters of the kinetic model, a genetic algorithm approach and then the Levenberg–Marquardt method are used. The statistical tests indicated that the estimated parameters and the present comprehensive kinetic model are significant and reasonable. The present model is validated at the range of operating conditions as 220–250°C, 15–25bar, H2/CO ratio of 1–2 and space velocity of 900–2300 1/h. It was found that the proposed model could correlate the experimental data well.