The online detection and control of concentration for agricultural greenhouse gas SO2 is an important technology to ensure normal agricultural production. This paper reports on a facile hydrothermal method to synthesis Pd-decorated and Pt-decorated MoSe2 nanomaterials, i.e. multistage flower-like structures with attached nanometallic particles and nanosheets hierarchical structures. The Pd/MoSe2 and Pt/MoSe2 hierarchical materials were characterized for the nanostructure, microscopic morphology and elemental compositions. The gas-sensing properties results show that the Pd/MoSe2 and Pt/MoSe2 nanofilm sensors have good sensitivity, stability and response rate to SO2 gas. The response values for the metal Pd and Pt decorated samples to 20 ppm SO2 were 2.04 and 3.42 times higher than those for the intrinsic MoSe2 samples at room temperature. The hierarchical flower-like structure proved to be beneficial in providing more adsorption drop points. In addition, based on the first-principles, the geometrical parameters and electronic properties of the metal-decorated modified structures were calculated to comparatively investigate the enhanced sensing mechanism of SO2 by nanoflower materials. The Pt-MoSe2 nanofilm sensor achieves a high sensitivity detection with a response value of 2.89 for low concentration (1 ppm) of SO2, which is confirming the promotion of charge transfer by metal decorating. This study suggests that Pd-MoSe2 and Pt-MoSe2 hierarchical structures may be recommended for the detection of the agricultural greenhouse gas SO2.