Oxide semiconductor In2O3 has been extensively used as a gas sensing material for the detection of various toxic gases. However, the pure In2O3 sensor is always suffering from its low sensitivity. In the present study, a dramatic enhancement of sensing characteristic of cubic In2O3 was achieved by deliberately fabricating p-n heterojunction-like NiO/In2O3 composite microparticles as sensor material. The NiO-decorated In2O3 p-n heterojunction-like sensors were prepared through the hydrothermal transformation method. The as-synthesized products were characterized using SEM-EDS, XRD, and FT-IR, and their gas sensing characteristics were investigated by detecting the gas response. The experimental results showed that the response of the NiO/In2O3 sensors to 600 ppm methanal was 85.5 at 260°C, revealing a dramatic enhancement over the pure In2O3 cubes (21.1 at 260°C). Further, a selective detection of methanol with inappreciable cross-response to other gases, like formaldehyde, benzene, methylbenzene, trichloromethane, ethanol, and ammonia, was achieved. The cause for the enhanced gas response was discussed in detailed. In view of the facile method of fabrication of such composite sensors and the superior gas response performance of samples, the cubic p-n heterojunction-like NiO/In2O3 sensors present to be a promising and viable strategy for the detection of indoor air pollution.