• The NiO/Zn 2 SnO 4 octahedrons were synthesized by a facile hydrothermal synthesis and subsequent wet impregnation process. • The sensor based on 3 mol% NiO loaded Zn 2 SnO 4 exhibited greatly enhanced sensing performance. • The ppb-level detection limit indicated its potential application. In this work, we successfully prepare the octahedral NiO/Zn 2 SnO 4 p-n heterostructure by a simple hydrothermal synthesis and subsequent wet impregnation process. The microscopic morphology characterization results show that the as-prepared composites are uniformly dispersed and have an octahedral structure with a size of 3−5 μm. The gas devices are fabricated and their sensing performances are investigated systematically. The response and selectivity of NiO/Zn 2 SnO 4 composites to acetone have been significantly improved than that of pure Zn 2 SnO 4 . Moreover, the response of the sensor to 100 ppb acetone is 1.4 at 300 °C, indicating that the detection limit is less than 100 ppb. The enhancement in sensing properties of composites is largely due to the p-n heterojunction formed by NiO and Zn 2 SnO 4 , which causes the transfer of carriers and the catalytic effect of NiO.