Designing high-performance triethylamine gas sensors with the stable gas response and low resistance variation in air under a wide relative humidity range is expected for human health and environmental surveillance. Here, a novel porous NiO/NiFe₂O₄fiber-in-tube nanostructure is prepared by the electrospinning process. The characterizations related to microstructure and surface morphology are carried out. Meanwhile, the gas sensing performance of the porous fiber-in-tube NiO/NiFe₂O₄materials is evaluated and compared systematically. The results indicate that the introduction of NiO as the second component can not only reduce the baseline resistance of NiFe₂O₄gas sensors dramatically but also optimize the gas sensing performance to a significant extent. Especially, the fabricated sensor based on the NiO/NiFe₂O₄fiber-in-tube with a Ni/Fe molar ratio of 1.5 exhibits the best performance. The gas response while detecting 50 ppm triethylamine at 300 °C is about 3.6 times higher than that with Ni/Fe molar ratio of 0.5. Moreover, the response values become more stable, and the baseline resistance has a lower variation under a wide relative humidity range, demonstrating the excellent humidity resistance. These phenomena might be ascribed to the distinctive fiber-in-tube nanostructure as well as the heterojunction between NiFe₂O₄and NiO.