The adsorption of naphthalene on Fe, Ni, Cu, Pt from aqueous solution has been measured using a recently developed radio‐tracer technique. The surface area of the metals was determined by the B.E.T. method using krypton. The amount adsorbed was found as a function of potential and concentration in solution. The results are discussed in terms of a “competition with water” model of the electrode‐solution interface, in which water molecules are treated as simple dipoles perpendicular to the metal. The same treatment applies to the adsorption of decylamine on the metals stated. The free energy of adsorption is calculated for each system and is related to the free energy of solution and the metal‐adsorbate dispersion interactions. Evidence for π‐bonding, particularly between naphthalene and platinum is given.