xDNA is an artificial duplex made of natural and benzo-homologated bases. The latter can be seen as a fusion between benzene and a natural base. We have used two different ab initio techniques, one based on B3LYP and a Gaussian expansion of the wave functions, and the other on GGA and plane-waves, to investigate the electronic properties of an xDNA duplex and a natural one with an analogous sequence. The calculations were performed in dry conditions, i.e., H atoms were used to neutralize the charge. It is found that the HOMO−LUMO gap of xDNA is about 0.5 eV smaller than that of B-DNA, independent of the technique used. The π−π* gap of xDNA is 1.3 or 1.0 eV smaller than that of B-DNA, depending on whether one uses B3LYP/6-31G or GGA/plane-waves, respectively. An analysis of how saturation changes the electronic properties of the nucleotide pairs that make up these duplexes suggests that different saturation schemes significantly affect the HOMO−LUMO gap value of xDNA and B-DNA. The same is not true for the π−π* gap. That xDNA has a smaller π−π* gap than B-DNA suggests that xDNA could be a plausible candidate for molecular-wire applications.