The solvated electron (e-aq) is a primary intermediate after an ionization event that produces reductive DNA damage. Accurate determination of standard redox potentials (E°) of nucleobases and of e-aq determine the extent of reaction of e-aq with nucleobases. In this work, E° of e-aq and of nucleobases have been calculated employing the accurate ab initio Gaussian-4 theory including the polarizable continuum model (PCM). The Gaussian-4-calculated E° of e-aq (-2.86 V) is in excellent agreement with the experimental one (-2.87 V). The Gaussian-4-calculated E° of nucleobases in dimethylformamide (DMF) lie in the range (-2.36 V to -2.86 V); they are in reasonable agreement with the experimental E° in DMF and have a mean unsigned error (MUE) = 0.22 V. However, inclusion of specific water molecules reduces this error significantly (MUE= 0.07). Employing a model of e-aq-nucleobase complex with 6 water molecules, reaction of e-aq with the adjacent nucleobase is investigated using approximate ab initio molecular dynamics (MD) simulations including PCM. Our MD simulations show that e-aq transfers to uracil, thymine, cytosine and adenine, within 10 to 120 fs and e-aq reacts with guanine only when a water molecule forms a hydrogen bond to O6 of guanine which stabilizes the anion radical.