This research provides conclusions that can partially cover the lack of knowledge related to the effects of ambient atmospheric conditions on DC electric power transportation. Two polymer insulating materials are used for completing this research study. Inside a climate chamber, the relative humidity is controlled and adjusted from 20% to 80% RH. Then, the samples are charged with positive or negative charges by applying ± 20 kV to the corona-generating ring of needles. The surface potential is measured using an electrostatic voltmeter and is converted into surface charge density later by applying the probe response matrix method. The pre-charged samples are then stressed with high-voltage negative or positive DC values inside the climate chamber over a range of controlled values of the surrounding air humidity until flashover takes place. The space charges, which can drift in the air gap to reach the solid surface, are highly affected by the level of the relative humidity of the surrounding air. Also, increasing humidity results in a reduction of the DC flashover inception voltage and a shorter time to flashover regardless of the voltage polarity. Moreover, the positive or negative flashover inception voltage of both materials increases with pre-deposited negative charges while it decreases with pre-deposited positive charges.