Dissolved gas analysis in transformer oil is useful for detecting early transformer failures. The research on gas sensors for monitoring dissolved gas in transformer oil has attracted wide attention from academia and industry. In this study, Rh-doped GeSe monolayers were used as gas sensing materials based on the density functional theory (DFT). The potential of the Rh-GeSe monolayer as a gas sensor was evaluated by calculating the geometric structure, adsorption distance (d sub/gas ), binding energy (E b ), adsorption energy (E ads ), transfer charge (ΔQ), the density of states (DOS), band structure, electron localization function (ELF), charge difference density (CDD), and sensitivity (S) of Rh-GeSe monolayer with eight gas molecules (SO 2 , C 2 H 2 , NO 2 , H 2 , CH 4 , CO 2 , H 2 S, and CO). The results show that the Rh-GeSe monolayer has a prominent response to SO 2 , C 2 H 2 , and NO 2 gas molecules and has great potential to become an excellent gas sensor. This study provides a theoretical basis for the application of Rh-GeSe monolayer in the field of gas sensing and provides a new way for the development of other gas sensors.