The treatment or upgrading of waste trifluoromethane (CHF₃, R23), which has a significant greenhouse effect, is of great importance in industry. Herein, series of SO₄²⁻/ZrO₂‐SiO₂ catalysts with different Brønsted and Lewis acid site densities and ratios were prepared for pyrolysis of R23 to tetrafluoroethylene (C₂F₄, TFE) and hexafluoropropylene (C₃F₆, HFP). The effects of impregnation concentration of (NH₄)₂SO₄ on specific surface area, crystal phase, and Brønsted and Lewis acid site densities and ratios were respectively demonstrated. The Brønsted and Lewis acid sites were observed to have cooperative effects on R23 transformation and up to 94.6% selectivity of (TFE + HFP) could be achieved at 750°C. The kinetic studies revealed the decomposition of R23 into CF₂ carbene and HF was the rate‐determining step, and a deactivation behavior was found due to the site coverage and pore blockage by the oligomers of TFE and HFP.