Constructing heterojunctions by using the synergistic and complementary effects of different metal oxide semiconductors (MOSs) properties can effectively increase catalytic activity, enhance adsorption capacity and improve carrier transport characteristics. Therefore, a series of NiO/SnO2 nanofibers with p-n heterojunction were prepared by coaxial electrospinning method, and triethylamine (TEA) detection was realized at low temperature or even room temperature by UV light (375 nm) photoactivation. Gas sensing measurements revealed that NiO/2SnO2 showed highresponse of 262 at 75 ℃ towards 50 ppm TEA, which is 6 times higher than that of pure SnO2. And NiO/2SnO2 based gas sensor has excellent repeatability and stability. The enhanced gas sensing mechanism was also discussed in detail, which is attributedto the synergistic effects aroused by p-n heterojunction and photoactivation. The present work provides a promising strategy for improving the gas sensitive characteristics of MOSs as well as a new idea for the development and application of room temperature TEA gas sensor.