At the very early time of irradiation, ballistic secondary electrons are produced as the most abundant of the radiolytic species directly within DNA or its environment. Here, we demonstrate the propensity of such low-energy (<3 eV) electrons to damage DNA bases via an effective loss of hydrogen located at the specific nitrogen positions. Since this site is directly implicated in the bonding of nucleobases within DNA and since dehydrogenation of the nucleic acid bases has been observed to be the predominant dissociative channel, the present findings foreshadow significant implications for the initial molecular processes leading to genotoxicity in living cells following unwanted or intended exposure to ionizing radiation (e.g., sunbathing, air travel, radiotherapy, etc.).