In this study, the optimization of Ni and Zr content in ZrO2-Al2O3 based catalysts prepared using the sol-gel method was performed to enhance the decomposition activity of CF4. The catalytic decomposition characteristics were investigated based on the methods of Ni addition (supported catalysts prepared by the impregnation method and synthesized catalysts employing synthetic approaches). Catalytic activity tests revealed that the decomposition activity at 700 °C varied by 5~10% depending on the Ni addition method, demonstrating the superior decomposition activity of the synthesized catalysts even with the same Ni and Zr content. XRD analysis and in situ DRIFT analysis using pyridine identified structural differences in the crystalline phases resulting from the Ni addition method. These structural variations led to an increased abundance of acidic sites, which served as active sites for the catalytic reaction. Long-term tests were performed for the impregnated and synthesized catalysts, confirming the superior durability of the impregnated catalysts. To evaluate the composition and chemical bonding states of the catalysts before and after the long-term tests, XPS analysis was performed. As a result, it was confirmed that an increase in the OAds/OTot ratio positively affects the catalyst durability.