In the present study, the pH-dependent radical-scavenging activities, in the TEAC (Trolox equivalent antioxidant capacity) assay, of pyridoxine (PN), pyridoxal (PL), pyridoxamine (PM) (vitamin B6 forms) and their main metabolite 4-pyridoxic acid (PA) was determined. For all compounds, the increase in the TEAC values with increasing pH of the medium from value 7 to 9 was observed. The order of radical-scavenging activity was found as follows: PN>PM>PL>PA and it was confirmed by their oxidative potentials measured using cyclic and square-wave voltammetry. Quantitative relationship between experimental radical-scavenging activity and calculated bond dissociation energy values (BDE) was found suggesting hydrogen atom donation as the main mechanism of radical-scavenging activity of vitamin B6 and PA. The results of the present study suggest that vitamin B6 may contribute to the total antioxidant capacity of antioxidants present in human body especially at basic conditions.