The biological relevance of Fe(II)/Fe(III) is becoming evermore apparent, especially in relation to its potential role in the progression of neurodegenerative diseases such as Parkinson's and Alzheimer's disease. The reported relationship between smoking and a reduced incidence of neurodegenerative disorders prompted this work. In order to investigate whether nicotine can interact with iron, we have studied the electrochemical behaviour of a Fe(II)/Fe(III) redox couple in the presence of nicotine. Solubility issues and lack of available nonreacting salts of nicotine necessitated studies being conducted at low pH values. Cyclic voltammetry experiments revealed a definite alteration in the electrochemical behaviour of the Fe(II)/Fe(III) redox couple suggesting the capability of nicotine to complex with free iron and, hence, reduce its reactivity. This is evident from a slower rate of heterogeneous electron transfer, ks, and a shift from reversible to quasi-reversible behaviour, as characterised from the diffusion coefficient (D), the full width half maximum (FWHM), DeltaEp and Ef. Additional complexation titrations, pH ranging from 1 to 7, confirm a weak complexation reaction occurring between Fe(III) and nicotine.