The adsorption of L-phenylalanine (Phe) at the Au(111) electrode surface has been studied using electrochemical techniques and subtractively normalized interfacial Fourier transform infrared (SNIFTIR) techniques. The electrochemical measurements of cyclic voltammetry, differential capacity and chronocoulometry were used to determine Gibbs energies of adsorption and the reference (E-1) and sample (E-2) potentials to be used in the spectroscopic measurements. The vibrational spectra have been used to determine: (i) the orientation of the molecule at the surface as a function of potential; (ii) the dependence of the band intensity on the surface coverage; (iii) the character of surface coordination, and (iv) the oxidation of adsorbed Phe molecules at positive potentials. The adsorption of Phe is characterized by DeltaG values ranging from - 18 to - 37 kJ mol(-1) that are characteristic for a weak chemisorption of small aromatic molecules. The electrochemical and SNIFTIR measurements indicated that adsorbed Phe molecules change orientation as a function of applied potential. At the negatively charged surface Phe is predominantly adsorbed in the neutral form of the amino acid. At potentials positive to the pzc, adsorption occurs predominantly in the zwitterionic form with the -COO- group directed towards the surface and the ammonium group towards the solution. At more positive potentials electrocatalytic oxidation of Phe occurs and is marked by the appearance of the CO2 asymmetric stretch band in the FTIR spectrum. Thus, relative to pzc, Phe is weakly chemisorbed at negative potentials, changes orientation at potentials close to the pzc and is oxidized at positive potentials.