Abstract: In this work, the first-principles calculations are used to study the gas-solid compatibility between new environment-friendly insulating gas CF₃SO₂F and the solid surfaces of common electrician equipment from a microscopic perspective. Firstly, the potential sites where the CF₃SO₂F molecule are prone to interact with solid surfaces are identified based on the frontier molecular orbital theory. Then, the interaction strength and charge transfer between CF₃SO₂F and five typical equipment solid surfaces are studied by computational simulation. At the same time, SF₆ is studied as the control group. Secondly, the origin of the similar gas-solid compatibility of CF₃SO₂F and SF₆ is revealed by further analysis. Finally, the dynamic compatibility of CF₃SO₂F with typical solid surfaces is investigated by molecular dynamics simulations. The results indicate that CF₃SO₂F has excellent compatibility similar to SF₆ because of similar electronic structures of active atom, especially in the electrical equipment whose contact surface is Cu, CuO, Al₂O₃ and epoxy resin coatings. Besides, CF₃SO₂F has poor compatibility with pure aluminum metal surface. The experimental results demonstrate the excellent compatibility of CuO and Al₂O₃ surfaces and support the validity of the selected computational method.