ZrO2-TiO2 mixed oxides with a Ti and Zr molar ratio of 1/1 were prepared under various conditions by the sol-gel method. Catalysts containing 5-35% H3PO4 were prepared using these oxides and the catalytic performance of each material for vapor-phase Beckmann rearrangement of cyclohexanone oxime to E-caprolactam was determined. As the H3PO4 content in the mixed oxide increased, the specific surface area decreased; XRD results indicated that ZrO2-TiO2 became amorphous after calcinations at 700 degrees C. The yield of lactam increased with increasing the H3PO4 content in the mixed oxide and reached a maximum value for the 15 wt.% H3PO4 on the ZrO2-TiO2 (1/1) support. With further increase in H3PO4 content, the lactam yield decreased; the lowest value was observed for the 35 wt.% H3PO4 on the ZrO2-TiO2 (1/1) support. The acidic properties and the pore characteristics of the catalysts were key factors that affected its performance. The influences of the operating parameters on the performance of H3PO4/ZrO2-TiO2 (1/1) catalyst were also investigated. The interaction of H3PO4 with Zro(2)-TiO2 (1/1) support has been investigated by FT-IR, for characterization of the interaction of H3PO4 with the support. (c) 2005 Elsevier B.V. All rights reserved.