Self-aldol condensation of cyclohexanone yields a mixture of 2-(1-cyclohexenyl)cyclohexanone (I), 2-cyclohexylidenecyclohexanono (II) and subsequent condensation products. An acid-treated clay catalyst was employed to selectively obtain the beta, gamma-unsaturated ketone (I). (I) was separated from the reaction mixture by fractional vacuum distillation and subsequently esterified with acetic acid to synthesise the corresponding ester, 2-(2-cyclohexyl acetate)cyclohexanone, a precursor of [1,1-biphenyl]-2,2＇-diol, which has applications in plasticizers, pesticides, as a diluent in epoxy resins, etc. The applicability of cation exchange resins and an acid-treated clay for the esterification of 2-(1-cyclohexenyl)cyclohexanone with acetic acid was explored.