This study establishes multi-scale correlations among molecular topology, adsorption behavior, and lubricating performance, based on two sulfonamide analogues (benzene-containing NPSA-SC and cyclohexyl-containing NCSA-SC). Compared to the stereo-adsorption configuration formed by the cyclohexyl-modulated NCSA-SC, the benzene ring structure in NPSA-SC promotes higher electron density and a more planar adsorption conformation. This leads to enhanced adsorption energy and the formation of a more stable, thicker adsorption film. This superior adsorption capability facilitates the compact assembly of molecules at the interface, effectively isolating the friction pairs. Simultaneously, it promotes the in-situ generation of friction film constituents with higher concentrations during the friction process, thereby ensuring durable lubrication performance. This research provides theoretical guidance for designing molecules with excellent adsorption and lubrication properties.