A series of TiO2/Al2O3 catalysts for cyclohexanone condensation have been prepared by impregnation method. Various characterization techniques, including XRD, BET, SEM, FT-IR, NH3-TPD, and Py-IR were applied to characterize their physical properties and chemical structures. The results show that the acidity of the TiO2/Al2O3 catalysts are all come from L-acid. In addition, the effects of reaction parameters such as TiO2 loading dosage, amount of cyclohexane, catalyst dosage, particle mesh, agitation rate, temperature and time were examined. The optimal reaction conditions were 40 ~ 60 particle mesh, 8% catalyst dosage, 393.15 K reaction temperature, 300 r/min agitation rate for 120 min with the conversion of cyclohexanone is 29.11% and close to 100% ultrahigh selectivity. Five cycles of reaction suggested the activity and selectivity of the catalyst did not change obviously and had potential industrial application value. Finally, the reaction kinetics was evaluated in cyclohexane under the reaction conditions of particle mesh 40 ~ 60 and 8% catalyst dosage and absence removing water produced, indicating the cyclohexanone self-condensation reaction was a second-order reaction.