Abstract. The intermetallic compound CaAu 2 Al 2 , and the members of the solid solutions SrAu 2-x Al 2+x (0 Յ x Յ 0.33) and Ba 3 Au 5+x Al 6-x (x = 0, 0.14, 0.49) were synthesized from the elements in sealed tantalum ampoules. The Ca compound crystallizes with the orthorhombic ThRu 2 P 2 type structure, whereas the targeted SrAu 2 Al 2 was found to form a solid solution according to SrAu 2-x Al 2+x . For the Ba system no "BaAu 2 Al 2 " was found, however, Ba 3 Au 5+x Al 6-x was discovered to crystallize in the monoclinic space group C2/c with its own structure type. The samples were investigated by powder X-ray diffraction and their crystal structures were refined on the basis of single-crystal