Herein, the adsorption of polystyrene (PS) on phenyl-modified SiO₂–Si substrates was investigated. Different from those for PS adsorption on a neat SiO₂–Si substrate, the growth rate (v_ads) in the linear regime and h_ads/R_g (h_ads, thickness of flattened and loosely adsorbed layers on the substrate; R_g, radius of gyration) declined with increasing molecular weight (M_w) of PS and the phenyl content on the modified substrates, while the thickness of the flattened layer (h_flat) and its coverage increased with increasing phenyl content. The results indicated that the adsorption of loose chains was controlled by the adsorption of flattened chains, as it only occurred in the empty contact sites remaining after the adsorption of flattened chains. Before approaching quasi-equilibrium (t < t_cross), the number of flattened chain contact sites increased due to an enthalpically favorable process and, correspondingly, their spatial positions dynamically changed, which perturbed the adsorption of loose chains. When the adsorption of flattened chains reached quasi-equilibrium (t > t_cross), the adsorption of loose chains was determined by the empty contact sites. The coverage of flattened chains and time to reach quasi-equilibrium were increased with more phenyl groups on the substrate, enhancing π–π interfacial interactions and resulting in a decreased adsorption rate and fewer loosely adsorbed chains. M_w-dependent v_ads and h_ads/R_g differed on phenyl-modified substrates compared to the neat SiO₂–Si substrate owing to fewer empty contact sites for loose chains. The study findings improve our understanding of the mechanism responsible for the formation and structure of the adsorbed layer on solid surfaces.