Designing hollow micro/nano structures for gas sensing materials is highly desirable for boosting gas sensing properties and still remains challenging, especially through a simple and economic way. Herein, porous In2O3 hollow nanorod (In2O3‐HNR), which was successfully fabricated by thermal decomposition of an In–MOF (CPP‐3) precursor, was applied as gas sensing materials. The pristine CPP‐3 and obtained In2O3‐HNR were systematically characterized by various techniques, such as XRD, SEM, TEM, TGA‐DTA, XPS, Raman and N2 physisorption. Characterization results indicated that the hexagonal rod‐like shape of original CPP‐3 was maintained after calcination, whereas the surface became rough and concave. In addition, the obtained In2O3‐HNR displayed a hollow interior with porous shell composed by In2O3 nanoparticles (9 nm). Taking advantage of this unique porous nanostructure, In2O3‐HNR exhibited a response as high as 6.2 to 5 ppm ethanol at operating temperature of 200 °C, fast response and recovery (3 and 4 s, respectively), and good selectivity to ethanol. The excellent ethanol‐sensing properties endow this In–MOF templated In2O3‐HNR material with a promising application in practical detection of ethanol gas. This method could be extended to the fabrication of other micro/nano structures with well‐defined morphology and composition for high‐performance gas sensing considering diversity of MOFs family.