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[Display omitted] • Cubic-like In 2 O 3 /α-Fe 2 O 3 composites assembled with porous nanoplates are obtained. • The introduction of Fe3+ component plays a vital role for morphological evolution. • In 2 O 3 /α-Fe 2 O 3 composites display superior TEA gas-sensing behavior at 170 °C. • In/Fe-2 shows the highest response and excellent cycling and long-term stability. • Sensing mechanism mainly depends on the unique microstructure and heterojunction. Cubic-like In 2 O 3 /α-Fe 2 O 3 heterostructures assembled with 2D porous nanoplates have been prepared by solvothermal method and subsequent calcination process. The introduction of Fe3+ component plays an important role for the morphological evolution of In 2 O 3 -based samples with unique crystal nucleation and growth mechanism. Compared with flower-like In 2 O 3 self-assemblies composed of tower-like structural units, In 2 O 3 /α-Fe 2 O 3 composites can display superior trimethylamine (TEA) gas-sensing behavior. For example, the optimal working temperature is reduced from 250 to 170 °C, and the response value of In/Fe-2 materials is 375.43, which is about 6.23 times than that of In 2 O 3 sensors. The enhanced gas-sensing properties are mainly attributed to large specific surface area (234.4 m2/g), the effective In 2 O 3 -α-Fe 2 O 3 heterojunctions, unique surface/interface effects, and tunable electron transmission mechanism. [ABSTRACT FROM AUTHOR]