In solution, DNA, the “most important molecule of life,” is a highly charged macromolecule that bears a unit of negative charge on each phosphate of its sugar-phosphate backbone. Although partially compensated by counterions (cations of the solution) adsorbed at or condensed near it, DNA still produces a substantial electric field in its vicinity, which is screened by buffer electrolytes at longer distances from the DNA. This electric field is experienced by any charged or dipolar species approaching and interacting with the DNA. So far, such a field has been explored predominantly within the scope of a primitive model of the electrolytic solution, not considering more complicated structural effects of the water solvent. In this paper, we investigate the distribution of electric field around DNA using linear response nonlocal electrostatic theory, applied here for helix-specific charge distributions, and compare the predictions of such a theory with specially performed, fully atomistic, large-scale, molecular dynamics simulations. Both approaches are applied to unravel the role of the structure of water at close distances to and within the grooves of a DNA molecule in the formation of the electric field. As predicted by the theory and reported by the simulations, the main finding of this study is that oscillations in the electrostatic potential distribution are present around DNA, caused by the overscreening effect of structured water. Surprisingly, electrolyte ions at physiological concentrations do not strongly disrupt these oscillations and are rather distributed according to these oscillating patterns, indicating that water structural effects dominate the short-range electrostatics. We also show that (i) structured water adsorbed in the grooves of DNA leads to a positive electrostatic potential core relative to the bulk, (ii) the Debye length some 10 Å away from the DNA surface is reduced, effectively renormalized by the helical pitch of the DNA molecule, and (iii) Lorentzian contributions to the nonlocal dielectric function of water, effectively reducing the dielectric constant close to the DNA surface, enhance the overall electric field. The impressive agreement between the atomistic simulations and the developed theory substantiates the use of nonlocal electrostatics when considering solvent effects in molecular processes in biology.