The promotion of nitrogen dioxide (NO2) sensing performance is obtained based on an Ag modified 1, 10-decanedithiol (DDT)/Au/n-GaAs Schottky diode. A semiconductor process and immersion treatment are employed in the device’s fabrication. The effects of Ag concentration and DDT molecules are studied by Fourier-transform infrared spectroscopy (FTIR). The interactions between NO2 gas molecules, Ag, and DDT are analyzed with X-ray photoelectron spectroscopy (XPS). The influences of the immersion Ag concentration, NO2 concentration, and operating temperature are investigated in this work. Experimentally, a high sensing response of 133.4 under 100 ppm NO2 ambience at 25 °C of the studied Ag/DDT/Au/n-GaAs device is obtained. In addition, the lowest detecting level (LDL) of 1 ppm NO2 gas at 25 °C is acquired for the studied device. The studied device also shows high selectivity toward NO2 gas at room temperature. Compared to some resistance-type and solid-electrochemical sensors, the studied device is suitable for low temperature operation.