Three α-alkene lubricants, differentiated by chain length, were selected as model compounds to investigate the influence of chain length on tribological properties. The novelty of this study lies in setting chain length as the sole variable to explore its impact on surface and adsorption energy. Based on the above findings, the study provides a unique explanation of the intrinsic relationship between chain length and tribological performance. The tribological properties of the three α-alkenes were compared, and subsequent characterization methods elucidated the wear mechanisms and explored tribochemical reactions. The study employed the Owens-Wendt-Rabel-Kaelble (OWRK) method and density functional theory (DFT) to investigate each compound's surface energy and adsorption energy. Experimental results revealed that the average friction coefficients (abridged as COF) for 1-decene, 1-tetradecene, and 1-octadecene decreased sequentially to 0.125, 0.099, and 0.075, respectively. The wear volume of 1-tetradecene decreased by 53.2% and that of 1-octadecene decreased by 64.0% compared to 1-decene. This can be attributed to the simultaneous enhancement of the surface energy and adsorption energy with increasing chain length. On the one hand, the increase in surface energy facilitates tribochemical reactions positively influencing the formation of tribofilms. On the other hand, the increase in adsorption energy enhances the adsorption of lubricants on the substrate surface. The synergy of these two effects allows 1-octadecene and 1-tetradecene (long-chain α-alkenes) to exhibit superior tribological performance compared to that of 1-decene (short-chain α-alkenes). Ultimately, this study offers unique insights into understanding lubrication mechanisms.