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Semiconductor oxide gas sensors have important applications in environmental protection, domestic health, and other fields. Research has shown that designing the morphology of sensitive materials can effectively improve the sensing characteristics of sensors. In this paper, by controlling the solvothermal reaction time, a unique hexagonal flower-like structure of In₂O₃ materials consisting of cuboid nanorods with a side length of 100–300 nm was prepared. The characterization results indicated that with the increase in reaction time, the materials exhibited significant morphological evolution. When the solvent heating time is 5 h, the flower-like structure is basically composed of hexagonal nanosheets with a thickness of several hundred nanometers and a side length of several micrometers. With the increase in reaction time, the apex angles of the nano sheets gradually become obtuse, and, finally, with the Ostwald ripening process, they become cuboid nanorods with side lengths of 100–300 nanometers, forming unique micro-flowers. Among them, the material prepared with a reaction time of 20 h has good sensing performance for NO₂, exhibiting low operating temperature and detection limit, good selectivity, repeatability, and long-term stability, thus suggesting a good application prospect.