Fe 2 O 3 ‐decorated CuO nanorods were prepared by Cu thermal oxidation followed by Fe 2 O 3 decoration via a solvothermal route. The acetone gas sensing properties of multiple‐networked pristine and Fe 2 O 3 ‐decorated CuO nanorod sensors were examined. The optimal operating temperature of the sensors was found to be 240°C. The pristine and Fe 2 O 3 ‐decorated CuO nanorod sensors showed responses of 586 and 1,090%, respectively, to 1,000 ppm of acetone at 240°C. The Fe 2 O 3 ‐decorated CuO nanorod sensor also showed faster response and recovery than the latter sensor. The acetone gas sensing mechanism of the Fe 2 O 3 ‐decorated CuO nanorod sensor is discussed in detail. The origin of the enhanced sensing performance of the multiple‐networked Fe 2 O 3 ‐decorated CuO nanorod sensor to acetone gas was explained by modulation of the potential barrier at the Fe 2 O 3 ‐CuO interface, highly catalytic activity of Fe 2 O 3 for acetone oxidation, and the creation of active adsorption sites by Fe 2 O 3 nanoparticles.