Li3AlAs2, Li3GaAs2 and Li3InAs2 were obtained from the elements via high temperature synthesis. Li3AlAs2 and Li3GaAs2 crystallize in a distorted 2.2.1 superstructure of the antifluorite structure type. The orthorhombic crystal structure is isotypic to Li(3)AIP(2) and Li3GaP2, space group Cmce (No. 64) showing layers of condensed TrAs4-tetrahedra (Tr- Al, Ga). Li3InAs2 crystallizes isotypic to Li3InP2 in a distorted 2.2.4 antifluorite type super- structure. The crystal structure is tetragonal, space group I4(1)/ acd (No. 142), showing a 3D-network of In4As10-supertetrahedra. Structural characterization by powder X-ray diffraction, thermal analysis, conductivity measurements and band structure calculations show ion conductivity for Li(3)InAs(2 )and electronic charge transport for Li3AlAs2 and Li3GaAs2.