Na2Ga7crystallizes with the orthorhombic space group Pnma(no. 62; a= 14.8580(6) Å, b= 8.6766(6) Å, and c= 11.6105(5) Å; Z= 8) and constitutes a filled variant of the Li2B12Si2structure type. The crystal structure consists of a network of icosahedral Ga12units with 12 exohedral bonds and four-bonded Ga atoms in which the Na atoms occupy the channels and cavities. The atomic arrangement is consistent with the Zintl [(4b)Ga]−and Wade [(12b)Ga12]2–electron counting approach. The compound forms peritectically from Na7Ga13and the melt at 501 °C and does not show a homogeneity range. The band structure calculations predict semiconducting behavior consistent with the electron balance [Na+]4[(Ga12)2–][Ga–]2. Magnetic susceptibility measurements show that Na2Ga7is diamagnetic.