Interfacial tension and surface excess isotherms for trioctylamine (TOA) were determined and interpreted. Despite its high hydrophobicity, TOA adsorbs at the hydrocarbon/water interfaces and decreases effectively the interfacial tension, especially in systems containing acidic aqueous phase. Interfacial activity of TOA rises with an increase of the aqueous phase acidity. The effect of amine protonation is clearly observed. Interfacial tension isotherms obtained experimentally can be well matched with the Szyszkowski equation. The interfacial activity of TOA is affected by the type of the organic diluent and the composition of the aqueous phase, i.e., the kind and concentration of nonorganic electrolyte present in the system.