The nature of the adsorption of a series of 2,2‘-substituted-1,1’-binaphthalenes over supported palladium and nickel catalysts has been studied. Adsorption has been shown to occur through the 2,2‘-substituted functional groups. Where this is not possible, no adsorption of the binaphthyl is observed. Adsorption of 2,2’-diamino-1,1’-binaphthalene occurred solely on the metal components of the catalysts. However, total coverage of the metal surface was not obtained, with only specific sites being available for adsorption. Adsorption of 2,2‘-dihydroxy-1,1’-binaphthalene occurred on the metal components but also spilled over onto the support. Adsorption was detected for 2-hydroxy-2‘-methoxy-1,1’-binaphthalene but no spill-over was observed, indicating that both hydroxy groups are involved in the spill-over process. Co-adsorption and sequential adsorption studies revealed that there are a variety of adsorption sites that favour different binaphthyls.