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Hydrogen sulfide (H2S) is the main component of sulfur hexafluoride (SF6) decomposition gas. Under the action of spectrum, H2S products volatilize rapidly, and the volatilization behavior is extremely obvious. Therefore, it is difficult to accurately analyze the content of H2S products in SF6 decomposition gas according to the spectral effect. Therefore, an online monitoring technology of SF6 decomposition gas based on infrared and ultraviolet spectral analysis is studied. The infrared measuring unit, ultraviolet measuring unit and multi-channel spectral pulse amplitude analyzer were connected together to detect SF6 decomposition components and determine SF6 decomposition gas components based on infrared and ultraviolet spectral analysis by distributing mixed gases. The gas separation characteristic function was established, the adsorption isotherm was defined according to the results of self-diffusion coefficient calculation, and the definition conditions of cation radial distribution were combined to standardize the specific monitoring algorithm execution flow. The experimental results show that the application of this monitoring technology can accurately define the content of H2S products in SF6 decomposition gas, and will not cause the problem of inaccurate monitoring due to volatilization of gas products even under the action of spectrum.