Various Pd-only three-way catalysts containing vanadium and zirconium oxides were prepared by the sol-gel method and investigated with XRD, XPS, V-51 NMR, Al-27 MAS NMR, Raman spectrometry, BET analysis and three-way catalytic reaction. In the Pd-only three-way catalyst prepared by the sol-gel method, vanadium and zirconium were good promoters to improve the resistance against SO2 poisoning and to enhance the thermal stability, respectively. Excellent properties such as high activity at low-temperature, improved durability against SO2 gas and enhanced thermal stability at high temperature were found only on the catalyst containing the specific mole ratio of V/Zr=0.36, Pd (1 wt.%)-V (2 wt.%)-Zr (10 wt.%)-Al2O3 catalyst, which was ascribed to some synergism between V and Zr like a formation of V-O-Zr bonds. Because of the synergism on the catalyst, the advantageous textural forms such as highly dispersed Pd clusters, Zr-O-X bond (X=V and Al), gamma -Al2O3 and amorphous tetrahedrally coordinated (M-O)(3)V=O were not deteriorated significantly to the disadvantageous textural forms such as large crystalline Pd clusters, monoclinic ZrO2, kappa -Al2O3 and theta -Al2O3, and microcrystalline octahedrally coordinated V2O5 species, in spite of thermal aging at 1000 degreesC.