•Copper complexation in herb infusions was examined by anodic stripping voltammetry.•Copper ligands ranged between 8.8 and 112.5μM.•Stability constants (logKapp) of copper ligands were in the range 6.3–8.7.•Organic matter was studied for the first time electrochemically in infusions.•Copper chelating capacity of infusions is partially attributed to specific organics. Complex formation is among the mechanisms affecting metals’ bioaccessibility. Evaluating the extent of interactions between trace elements and several constituents of food items is of great interest. This paper examines the release of copper-complexing ligands in herbal infusions of 13 aromatic plants commonly used in Greece. The concentration of ligands (LT) and the copper-binding strength (logKapp) of herbal infusions were determined with Differential Pulse Anodic Stripping Voltammetry (DPASV). All herbal infusions were found to release Cu complexing ligands, at concentrations ranging from 8.8 to 112.5μM in rosemary and marjoram, respectively. In all infusions the total copper concentrations were lower than the corresponding LT values, indicating that Cu is fully complexed. Aiming to partially characterise the physico-chemical properties of the released organic material, the surface active substances (SAS), reduced sulphur species (RS) and catalytically active compounds (CAC) were measured, for the first time, in herbal infusions by sensitive electrochemical techniques.