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Real-time monitoring of SF6 status is of exceptional importance to ensure stable operation of the power system, to promptly diagnose whether an insulation failure has occurred and to assess the severity. Considering the excellent physicochemical properties and insulation defects of hexagonal boron nitride, the strategy of surface modification, namely, hydrogenation, fluorination, and combinations of the two ways, is proposed to improve its chemical activity, and the gas-sensing potential of the most effective one is investigated using density functional theory. The typical adsorption models of SF6 decomposition component gases on the surface of F-BN-H are constructed, and the most stable adsorption structures with their density of states, molecular orbitals, and sensing responses are analyzed. The results show that F-BN-H has good sensitivity to decomposition components of SF6. To be specific, SO2 and SOF2 have good adsorption properties, prominent charge transfer, and distinct change in electronic properties. The response of gas adsorption can be detected timely by the change in conductivity, and, additionally, the adsorbent has fast desorption capacity at room temperature. These results indicate that the F-BN-H-based gas sensor is a qualified potential candidate with dependable application and recoverability for detecting SF6 decomposition in high-voltage insulated equipment. [ABSTRACT FROM AUTHOR]