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This paper reports the facile synthesis of α-Fe2O3 nanoellipsoids by a low-temperature hydrothermal process and their effective utilization in the fabrication of a highly sensitive aqueous ammonia chemical sensor by the I–V technique. The as-synthesized α-Fe2O3 nanoellipsoids are characterized in terms of their morphological, structural and optical properties. The detailed structural and optical properties confirm a rhombohedral α-Fe2O3 structure and indirect (1.87 eV) and direct (2.15 eV) band gaps, respectively, for the synthesized nanoellipsoids. The fabricated aqueous ammonia sensor based on nanoellipsoids exhibits a very high and reproducible sensitivity of ∼4.678 µA cm−2 mM−1 and a detection limit of ∼0.04 nM with a correlation coefficient (R) of 0.995 in a short response time (10.0 s). The presented work demonstrates that simply synthesized iron oxide nanostructures can efficiently be used for the fabrication of reliable and reproducible chemical sensors.