Gold nanobelts were synthesized by directional solidification of the Fe-Au eutectoid followed by selective phase dissolution. Cleaning from organic molecules was performed in alkaline solution by PbO(2) deposition/dissolution to avoid surface reconstruction. The electrochemical behaviour of the Au nanobelts was determined by structure-sensitive electrochemical reactions, and the findings confirm the results obtained by selected area electron diffraction (SAED). The underpotential deposition (UPD) of lead under alkaline conditions and cyclic voltammograms (CVs) in sulphuric acid revealed an unusual large amount of (110) domains (>65%). Finally, after cleaning the Au nanobelts showed a higher and stable electrocatalytic behaviour toward methanol oxidation in alkaline media. The possible mechanism and the potential applications of the Au nanobelts are discussed.