Catalysts based on different halo‐alkanes structures with durable catalytic performance were synthesized and applied to the Friedel–Crafts alkylation of long‐chain alkenes (mixed C16–24 olefins) with toluene. Surprisingly, compared with the usual industrial catalysts (~10 runs), the cyclic times of the ionic liquid (IL) catalysts reached up to 24 runs, which greatly promotes the industrialization process. Then, Lewis acids of catalysts with different precursor/AlCl3 molar ratios were investigated and a close relation was discovered between the Lewis acid and catalytic activity. In addition, a comparison of the different halo‐alkanes structures about those catalysts was made. The results showed that the [C6Et3N]Cl–AlCl3 had the strongest Lewis acid, corresponding to the highest catalytic performance. Also, the structures of precursors and the specific gravity and active site species of catalysts were investigated by Fourier transform infrared and Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Meanwhile, the various parameters (catalyst dosage, toluene/olefin molar ratio, reaction temperature and reaction time) of long‐chain alkenes alkylation with toluene were studied. Finally, under the optimized reaction conditions, the conversion and selectivity of long‐chain alkenes alkylation reached 99.92 and 32.99%, respectively.