The invention relates to a method for photoelectrically detecting nitrogen dioxide with trace amount. A resistive sensor comprises a ceramic substrate, a fixed electrode, a sensitive material, a heater, a thermocouple, a signal processor and a light source. By utilizing the photoconductive effect of the sensitive material of the resistive sensor, light with a 200-800nm wavelength range is irradiated onto the sensitive material, and the nitrogen dioxide with the trace amount is detected through the change in resistance of the sensitive material, so that the NO2 detection limit is improved and simultaneously the working temperature is reduced. The method not only can improve the detection limit (reach ppb level), but also reduces the working temperature (room temperature to 220 DEG C).