CF₄, one of the Perfluorocompounds (PFCs), also known as a greenhouse gas with high global warming potential. In this study, Zr/γ-Al₂O₃ catalysts were developed for CF₄ decomposition. The addition of Zr onto γ-Al₂O₃ achieves a high CF₄ conversion efficiency of 85% at 650 °C and maintain its activity for more than 60 h, which is obviously higher than that of bare γ-Al₂O₃ (50%). The mechanism involved in CF₄ decomposition over the Zr/γ-Al₂O₃ are clarified that the surface Lewis acidity sites are the main active center for CF₄ directly adsorbing and decomposing. The results of NH₃-TPD and FT-IR analyses suggest that the amount of Lewis acidity sites on catalyst surface increases significantly after the introduction of Zr, thereby enhancing the activity of catalyst for CF₄ decomposition. The results of XPS analyses confirms the electrons transfer from Zr to Al, which contribute to the increase in Lewis acidity sites. The results of this work will help the development of more effective catalysts for CF₄ decomposition.