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The construction of p-n heterostructures using n-type and p-type semiconductor is a very important way to enhance gas sensing performance. In this work, hexagonal rod-shaped NiCo2O4/In2O3 with larger surface area was prepared via a simple water bath approach and subsequent calcination process. The microscopic morphology characterization results show that the NiCo2O4/In2O3 composite has a hexagonal hollow rod-shaped structure, where NiCo2O4 grows in situ on the surface of In2O3, forming p-n heterojunctions. Notably, the NiCo2O4/In2O3 composites formed with 6% NiCo2O4 addition (In-NC6) at 200 °C showed the best gas sensing performance for 1 ppm formaldehyde with a response value of 9.11 and a theoretical detection limit as low as 10.83 ppb. The rich oxygen vacancies, active site and p-n heterojunction are conducive to the adsorption of formaldehyde and electron transfer. This in situ growth approach provides novel ideas and promising prospects to synthesize other p-n heterojunction mate ....