The development of fast-response, high sensitivity and selectivity gas sensors for monitoring of organophosphorus is essential, where two dimensional graphene-based materials possessing exceptionsal carrier mobility are considered as promising candidates for room-temperature organophosphorus detection. However, it is challenging to fabrication of graphene-based gas sensors for detection of organophosphorus with excellent sensing performances. Herein, we develope a self-redox strategy to synthesize polypyrrole decorated-reduced graphene oxide hybrids (PPy-rGO) by redox reactions between pyrrole and GO during hydrothermal treatment process. This self-redox strategy results in the formation of perfact interfical strucutre between PPy and rGO through the π-π interactions without the impurity from the conventional oxidation/reducing agents. Most importantly, such PPy-rGO hybrids can be used as novel sensing materials for detection of dimethyl methylphosphonate (DMMP) at room temperature. Specially, the response of PPy-rGO-based sensor towards 100 ppm DMMP can reach 12.9 %, which is 3-fold higher than that pristine rGO-based sensor. Meanwhile, PPy-rGO-based sensor exhibits short response time/recovery time (43 s/75 s), low detection limit (5 ppm), excellent repeatability, and high selectivity. By combination of FT-IR and N2 sorption isotherms, the enhanced DMMP sensing performances of PPy-rGO hybrids are concluded as following two aspects. Firstly, the formation of hydrogen bonds between PPy-rGO hybrids and DMMP molecules regulates the adsorption/desorption of DMMP. Secondly, increasing BET surface area by introduction of PPy into rGO matrix is beneficial to DMMP diffusion among the sensing materials. Our work would offer a new strategy for rational development of graphene-based materials for detection of organophosphorus at room temperature.