Despite the tremendous importance of so-called ionizing radiations (X-rays, accelerated electrons and ions) in cancer treatment, most studies on their effects have focused on the ionization process itself, and neglect the excitation events the radiations can induce. Here, we show that the excited states of DnA exposed to accelerated electrons can be studied in the picosecond time domain using a recently developed cathodoluminescence system with high temporal resolution. our study uses a table-top ultrafast, UV laser-triggered electron gun delivering picosecond electron bunches of keV energy. this scheme makes it possible to directly compare time-resolved cathodoluminescence with photoluminescence measurements. This comparison revealed qualitative differences, as well as quantitative similarities between excited states of DnA upon exposure to electrons or photons. Most studies on the effect of so-called ionizing radiations (X-rays, electrons, ions) have focused on the ionization process itself. However, ionizing radiation can also efficiently induce excitations in various molecules, whose effects are rarely studied in radiation chemistry and biochemistry. In particular, there is very little literature on the excited state dynamics of DNA following the initial energy deposition by charged particles. For example, highly energetic excited states can be produced by energetic electrons (as suspected from electron energy-loss spectroscopy on DNA 1,2 , showing a "plasmon band" at 25 eV) with expected, associated short lifetimes 3 , and putative damaging effects when they cause molecular reorganization. Furthermore, such states may migrate, potentially changing the dose distribution locally. One way to identify and study such states is to analyse their luminescence. The luminescence of DNA under ionizing radiations (also called scintillation) has been reported in the literature-albeit scarcely-especially at low temperatures. For instance, in frozen DNA, a microsecond 4.3 MeV electron excitation induced a "short-lived" emission extending up to 530 nm 4. More recently, "in-pulse" nanosecond (ns) luminescence spectra of irradiated (260 keV electrons) wet and dry DNA 5-7 showed the same broad emission that is sensitive to the presence of energy or electron traps. A negligible amount of light is emitted after the ns pulse, leading to the suggestion that excited states form by geminate recombination of electrons and holes and/or by direct excitation, with sub-ns relaxation times. Further progress on this topic has been impaired by the lack of appropriate time-resolved sources of ionizing radiation. The so-called pulsed radiolysis technique relies on a high-energy particle accelerator, which has two drawbacks 4 : (i) it has a low repetition rate (a few hundred Hz at the most) that is not compatible with ultrafast time-resolved techniques, such as time-correlated single photon counting, and limits the time resolution to the ns range 8 ; (ii) it provides high-energy beams that produce Cerenkov light, which blinds the detector 9,10...