The development of metal oxides-based gas sensors for DMMP detection simultaneously possessing low operating temperature, low limit of detection and high sensitivity remains formidable challenges. In this work, a facile and efficient colloidal assembly approach is proposed to prepare Au modified SnO2 hybrids (Au-SnO2) with perfect metal-semiconductor interface and successfully used in DMMP detection application. After optimization, the best DMMP sensors based on Au-SnO2 hybrids display outstanding sensing performances, including high response (1.88 to 680 ppb DMMP), low operating temperature (200 °C), extremely low limit of detection (34 ppb), as well as short response/recovery time (25 s/72 s). The sensing mechanism analysis reveals that the excellent sensing performances are mainly attributed to the synergy of chemical oxidation of DMMP catalyzed by Au-SnO2 hybrids and physical adsorption of DMMP by hydrogen-bonding interactions. The present work not only provides an insight into the DMMP sensing mechanism, but also offers a promising general approach for development of high-performance gas sensors.