This study examined the relation between the acid-base properties of a binary oxide, TiO2-ZrO2, and the reaction behavior of various C-6 hydrocarbons over this mixed oxide. Based on experimental results, both the strong acid sites and the strong base sites performed as cracking sites and could be poisoned by doping a small amount of K2O and B2O3, respectively. It was demonstrated that the paired acid-base sites played most important roles on dehydrogenation of cyclohexane and cyclization of n-hexane and hexene. Both the yield and selectivity of benzene increased with the relative paired acid-base amount. The results of isomerization of 1-hexene showed that the yield of the molecular isomerization increased at the expense of the double bond migration as the relative acid/base ratio increased. The results also showed that 2-hexene had a much higher aromatization rate than 1-hexene over TiO2-ZrO2 catalysts. A detailed reaction mechanism of the aromatization C-6 hydrocarbons over an acid-base bifunctional catalyst is proposed, which was different from the mechanism of a conventional metal-acid bifunctional catalysts.