This work reported a comparative analysis of the amperometric responses of antigen-antibody reactions on two stable chiral surfaces which were modified with 1,2-diphenylethylenediamine enantiomers. Alpha-fetoprotein antibody and antigen (anti-AFP and AFP) were selected as model systems. First, (1R,2R)-1,2-diphenylethylenediamine or (1S,2S)-1,2-diphenylethylenediamine was modified on the gold surface of the electrode through amide linkage to construct chiral surfaces. Then, anti-AFP was immobilized on the chiral electrode surface by electrostatic and hydrogen bonding interactions. The electrochemical characteristics of the modified electrodes were studied via cyclic voltammetry. The selective current responses of antigen-antibody reactions on chiral electrode surfaces for different incubation time and varying AFP concentrations were monitored. The antigen-antibody reactions were greatly influenced by the chirality of 1,2-diphenylethylenediamine enantiomers, and the amperometric responses obtained from the (1S,2S)-1,2-diphenylethylenediamine modified electrode was obviously stronger than that from the (1R,2R)-1,2-diphenylethylenediamine modified electrode. Such work may not only offer valuable reference to the research of chiral drugs, but also help to comprehend the high selectivity of chiral molecular species in biosystems. Copyright © 2011 John Wiley & Sons, Ltd.