The novel nanocomposites were obtained by covalently linking arginine enantiomers with the sidewall of multi-walled carbon nanotubes, and utilized as sensing materials for biomolecular recognition in electrochemical immunoassay. They were characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and circular dichroism spectroscopy (CD). Nano-gold and Prussian Blue were employed to amplify the analytical signal responses. Prostate specific antibody/antigen and carcinoembryonic antibody/antigen were used as model systems. The results showed that the different configurations of nanocomposites could readily facilitate chiral recognition of antibodies, and D-nanocomposites displayed a larger signal.arginine, multi-walled carbon nanotubes, chiral nanocomposites, recognition, electrochemical immunoassay