During a systematic search of the RE-Au-Sn (RE = La, Ce, Pr, Nd) ternary phase space, a series of compounds with the general formula REAu1.5Sn0.5 have been identified. These phases can be synthesized by arc melting the elemental metals, followed by annealing. The crystal structures were solved using single-crystal X-ray diffraction, with the composition confirmed by energy-dispersive X-ray spectroscopy. All four compounds crystallize in orthorhombic space group Imma with the CeCu2-type structure. Most notable in these compounds is the polyanionic backbone composed of a single statistically mixed Au/Sn position, which creates a puckered hexagonal bonding network separated by the rareearth atoms. Electronic structure calculations indicate that the Au 5d bands are in the density of states, while the crystal orbital Hamilton population (-COHP) curves demonstrate Au-Au and Au-Sn interactions, which stabilize the crystal structure. Likewise, a qualitative electron localization function analysis supports the existence of a polyanionic network, and a Bader charge analysis implies anionic character on Au and Sn. The preference for these compounds to adopt the simple CeCu2-type structure is also determined using density functional theory calculations and compared to related compounds to establish a better picture of the unusual behavior of Au in polar intermetallic compounds.