The role of SF6 in gas-insulated equipment is crucial for insulation and arc extinction. When subjected to electrical faults, thermal faults, and mechanical failures in insulation devices, SF6 can decompose into H2S, SO2, SOF2, and SO2F2. This study conducted first-principles simulations to analyze the effect of Cun (n = 1–3) cluster-modified monolayer WSe2 on sensing H2S, SO2, SOF2, and SO2F2 gases during SF6 decomposition. The optimal doping positions of Cun-WSe2 clusters at n = 1, 2, and 3 were determined, showcasing their superiority over pure WSe2 in terms of band gap, frontier orbitals, and density of states. Subsequently, a detailed investigation was carried out on the adsorption effects of the four gases at the optimal doping positions, including parameters such as adsorption distance, adsorption energy, charge transfer, differential charge density, and density of states. It was found that when the number of copper atoms in the cluster increased to 3, the banding energy sharply rose to -2.395 eV. Simulation results demonstrated the adsorption behavior of H2S on Cun (n = 1–3)-WSe2 demonstrates remarkable affinity, with an increasing adsorption energy as the number of Cu atoms rises. Notably, Cun (n = 1–3)-WSe2 exhibits favorable desorption times for SO2. At 378 K, the desorption time for SO2@Cu3-WSe2 is 14.7 s. At 498 K, desorption times for SO2@Cu1-WSe2 and SO2@Cu2-WSe2 are 7.59 s and 2.85 s, respectively. When the number of copper atoms is 2, the cluster-modified system desorbs SOF2 at room temperature in only 0.89 s. Moreover, Cun (n = 1–3)-WSe2 displays strong adsorption towards SO2F2, characterized by prolonged desorption times, rendering it a promising adsorbent for SO2F2 removal. This study aims to highlight the adsorption effects of different numbers of Cu atomic clusters in the Cun-WSe2 system on SF6 decomposition gas, further advancing research for developing high-performance SF6 decomposition gas sensors.