In this work, we employ electron spin resonance (ESR) spectroscopy to investigate the effects of temperature on excess electron and hole transfer through DNA. The competitive processes of tunneling, protonation at carbon, and hopping are investigated in hydrated DNA solids (hydrated to 14 waters/nucleotide) and frozen glassy aqueous (D 2 O) solutions of DNA intercalated with mitoxantrone (MX) at temperatures from 4 to 195 K. Monitoring the changes in the ESR signals of MX radicals, one-electron oxidized guanines (G •+ ), oneelectron reduced cytosines [C(N3)D • (CD • )], thymine anion radicals (T •-), and irreversibly deuterated thymine radicals [T(C6)D • (TD • )] with time at different temperatures allows for distinguishing the thermal barriers of each process. The tunneling of electrons from DNA radicals to MX is found to be the dominant process at temperatures less than or equal to 77 K. The value of the average tunneling distance decay constant, β avg , is found to be the same at 4 and 77 K. Working with hydrated DNA allows the distinction between electron adducts to cytosine and those to thymine, a distinction not possible in glassy systems. In the solid hydrated DNA, we find that CD • does not undergo significant electron loss in the time of our experiments below 170K and that electron tunneling in DNA is mainly from T •-. Irreversible deuteration of T •at carbon position 6, which results in TD • , begins at 130 K and increases in relative fractions of the radicals as temperature increases. Hole and electron hopping resulting in the recombination of G •+ and CD • are not substantial until temperatures near 195 K are reached. Above 130 K, the tunneling processes are not competitive with deuteration of T •-, and above 170 K, they are not competitive with recombination, which presumably results via activated excess electron hopping.