The new compound Ca3AlSb3 crystallizes in the orthorhombic system (space group Pnma (No. 62)) with lattice constants a = 1283.5(5) pm, b = 448.9(2) pm , c = 1428.2(5) pm In the structure there are AlSb4 tetrahedra connected by common corners to form chains. The new compound Ca5Al2Bi6 crystallizes in the orthorhombic system, too (space group Pbam (No. 55)) with lattice constants a = 2333.3(8) pm, b = 758.2(3) pm, c = 452.9(2) pm AlBi4 tetrahedra are connected by common corners and Bi2 groups to form double chains. Both compounds are classified as Zintl phases.