•A facile manufacturing process of new Rb2CO3-decorated In2O3 sensor.•The Rb2CO3/In2O3 composite sensor detecting 100 ppb level NO2 gas at room temperature under visible light illumination.•Propose the mechanism for the high sensing performance realized by high rate of electron supply to the receptor.•Good sensing performance of high selectivity, stability, repeatability, linearity, with discussion of the humidity effect. The Rb2CO3-decorated In2O3 sensor is prepared for detection of NO2 at room temperature under light irradiation. Physical and chemical properties of the materials and structures are thoroughly investigated by various analytical tools of scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy, thereby confirming the formation of the Rb2CO3/In2O3 p-n junction at the interface. The Rb2CO3-decoration effect on In2O3 sensor is examined under light irradiation of different wavelengths and intensities. Rb2CO3-decoration exhibits much higher sensing performance than pure In2O3 sensor, and furthermore, the visible light irradiation improves in the response level and sensing kinetics. The sensor detects less than 100 ppb NO2. In addition, the Rb2CO3-decorated In2O3 sensor shows high selectivity, stability, repeatability, and linearity. The ultimate performance of the nanostructured sensor is elucidated by the depletion model of the conduction type gas sensors. The effect of humidity on the sensing performance is also investigated.