A kind of novel amphiphilic silica-based nanoparticle having surface-bound octanoyl-aminopropyl moieties (OA-NP) with the diameter of similar to 250 nm was successfully prepared and characterized by elemental analysis, Fourier transform infrared spectrometry. The potential use of OA-NP as pseudostationary phase in capillary electrochromatography for the separation of aromatic acids, basic, and neutral compounds was investigated. Five aromatic acids were separated rapidly with high column efficiency as they migrate in the same direction with the EOF under optimum experimental conditions. Under a running buffer with the composition of 40% methanol, 10 mM phosphate buffer (pH 5.5) with 1.0 mg/mL OA-NPs added, basic compounds investigated were baseline resolved with relatively symmetrical peaks. Due to the existence of polar acyl amide group on the surface of OA-NPs, "silanol effect'' that occurs between the positively charged basic analytes and the silanols of the capillary column was greatly suppressed. Furthermore, the newly synthesized OA-NPs were also tried for the separation of some neutral analytes, and satisfactory separations were obtained.