A highly sensitive flow-injection capacitive immunosensor was developed for detection of the mycotoxin zearalenone (ZEN). Different strategies for immobilization of an anti-ZEN antibody on the surface of a gold electrode, i.e. polytyramine or self-assembled monolayers (SAMs) of 3-mercaptopropionic acid (3-MPA) and lipoic acid (LA), were used and their performances were compared. The LA- and 3-MPA-based systems showed broad linear ranges for ZEN determination, i.e. from 0.010 nM to 10 nM and from 0.020 nM to 10 nM, respectively. Under optimal conditions, the LA-based immunosensor was capable of performing up till 13 regeneration-interaction cycles (with use of glycine HCl, pH 2.4) with a limit of detection (LOD) of 0.0060 nM, equivalent to 1.9 pg mL−1. It also demonstrated a good inter-assay precision (RSD < 10%). However, the tyramine-based capacitive immunosensor showed a bad repeatability (only 4 regeneration-interaction cycles were possible) and inter-assay precision (RSD > 15%) which did not allow sensitive and precise measurements. The LA-based method was compared with a direct ELISA. These results demonstrated that the label-free developed capacitive immunosensor had a better sensitivity and shorter analysis time in comparison with the direct microwell-plate format.