The key challenge to develop gas sensors with high performances lies in the novel design of superior functional materials for effective reactions between target gases and sensing layers. Metal–organic frameworks (MOFs) have emerged as versatile candidates for preparation of ideal nanostructured materials with controllable composition, various structures and tunable pore size. Herein, a series of Fe–based and Fe/Ni–based one–dimensional (1D) nanostructures using MOFs as templates were prepared systematically. As a result of the hollow structure and nanohybrid features, the optimized α–Fe₂O₃/NiFe₂O₄nanotubes can exhibit high specific surface area (118.03 m² g⁻¹) and provide a mass of active sites compared to individual components (α–Fe₂O₃ nanowires and NiFe₂O₄ nanowires), which is beneficial to improve the response (R_a/R_g = 23) to acetone vapors. In addition, the smart design also endows the sensor based on α–Fe₂O₃/NiFe₂O₄ nanotubes with good selectivity, fast response time (4 s) and long–term stability (30 days). In this work, the advantages of 1D hollow heterogeneous materials will provide a new perspective of MOF–derived nanostructures for the particular application in acetone gas sensors.