Adsorption and orientation modes of pyridine adsorbed on nickel in at pH 3.5 are discussed based on surface‐enhanced Raman scattering (SERS) spectroscopy. The SERS spectra of pyridine adsorbed on nickel were recorded on a Raman spectrometer with a SERS‐active silver electrode covered with a thin layer of electrodeposited nickel. It is concluded that a pyridine molecule is perpendicularly chemisorbed on the nickel surface by the formation of a nickel‐nitrogen σ‐bond.