The fabrication of heterostructure has been considered as a great potential to improve the gas sensing performances due to its flexible features at the interface. The p-n heterojunction composites with Co3O4 modified In2O3 were synthesized through physical mixing calcination process and hydrothermal method for the effectiveness comparison as gas sensors for detecting of ethanol. The morphology, microstructure, and surface element state of the heterojunction materials were investigated. Furthermore, the forbidden band width and the active oxygen species were analyzed on account of the efficient interface for the heterojunction materials. The gas response of heterojunction sensor by the physical mixing calcination method exhibits an outstanding response of 5585 towards 100 ppm of ethanol gas, which was about 10 times higher than that by two-step hydrothermal method. Moreover, it shows improved adsorption and desorption kinetics with response time of 8 s and 15 s, respectively at the operating temperature of 280 °C. It also reveals a distinct selectivity to ethanol with better reproducibility, the humidity-dependent stability and ambient retention over a period of 30 days with rendering 94 %. Combined with the in-situ infrared diffuse reflection spectrum analysis and Hall effect test from the perspective of catalytic and electrical properties, we inferred the gas sensing enhancement mechanism involved in In2O3Co3O4 p-n heterojunction with the design of proof-of-concept demonstration by surface modification, which could provide an approach to explore the effect of heterojunction interface through the variable method.