Nanoparticle (NP)–surfactants formed by the self-assembly of NPs and end-functionalized polymers at the hydrophilic/hydrophobic interface have a wide range of applications in many fields. In this study, the influence of density of amino groups, NPs dimension and pH on the interaction between end-functionalized polymers and NPs were extensively investigated. Single amino-terminated polystyrene (PS-NH2, Mw ≈ 0.6k, 2.5k, 3.5k, 3.9k) and diamino-terminated polystyrene (H2N-PS-NH2, Mw ≈ 1.1k, 2.8k) were prepared using reversible addition–fragmentation chain transfer polymerization and atom transfer radical polymerization. NPs with different dimensions (zero-dimensional carbon dots with sulfonate groups, one-dimensional cellulose nanocrystals with sulfate groups and two-dimensional graphene with sulfonate groups) in the aqueous phase were added into the toluene phase containing the aminated PS. The influence of pH and the molecular weight of amino-terminated PS on the interfacial tension between two phases were investigated. The results indicate that aminated PS exhibited the strongest interfacial activity after compounding with sulfonated NPs at a pH of 3. Terminating PS with amino groups on both ends leads to better performance in in reducing the water/toluene interfacial tension than modifying the molecular structure of PS on a single end. The dimension of sulfonated NPs also contributed significantly to the reduction of the water/toluene interfacial tension. The minimal interfacial tension was 4.49 mN/m after compounding PS-NH2 with sulfonated zero-dimensional carbon dots. Molecular dynamics simulation on the evolution of the water/toluene interface in the presence of sulfonated carbon dots and H2N-PS-NH2 revealed that these opposite charged substances moved towards the interface in an extreme short time and orderly assembled in a thermodynamic equilibrium.