Single molecule DNA sequencing requires new approaches to identify nucleotide bases. Using molecular dynamics simulations, we investigate the intrinsic electrostatics of single-stranded DNA by solving the nonlinear Poisson–Boltzmann equation. The results show variations of the molecular electrostatic potential (MEP) within 3 nm from the center of the sugar backbone, with suitably differentiable variations at 1.4 nm distance. MEP variations among four nucleotide bases are the most significant near ~ 33.7° and ~ 326.3° angular orientation, while the influences of the neighboring bases on MEPs become insignificant after the 3rd-nearest neighbors. This analysis shows potential for direct electronic sequencing of individual DNA molecules. [Formula: see text]Special Issue Comment: This paper about DNA sequencing based on molecular electrostatic potential maps of the DNA in the channel is related to the Special Issue articles about: measuring enzymes,32 and solving single molecules' trajectories with the RDF approach33 and with the QuB software.34