Na2Au3A1, the first experimentally prepared compound in the ternary Na-Au-Al system, crystallizes in the cubic crystal system with space group P4(1)32 (a = 771.42(2) pm). It can be described as a P-centered ternary ordered variant of the F-centered Laves phase MgCu2 and is isostructural to Mo3Al2C. A phase width was found for the series Na2Au4-xAlx allowing a successive substitution of Au by Al. The primitive structure forms for x >= 0.5. Na(2)Au(3)A(1) is diamagnetic at room temperature but metallic in nature, as seen from susceptibility and electrical resistivity measurements. Band structure calculations and X-ray photoelectron spectroscopy confirm the metallic nature of the title compound as states are found at the Fermi level of the DOS, along with its "auride" character. Na-23 and Al-27 solid-state-NMR. investigations show the existence of both a disordered (x = 0.5 and 0.75) and a fully ordered (x = 1.0) representative within this series. Both COHP and Bader charge analyses suggest the presence of strong Au-Al interactions forming an anionic [Au3Al](delta-) network, with the Na cations occupying the cavities.