In our recent work, we demonstrated the potential stability and synthesizability of mixed compounds along the solid solution Na1+xZnxAl1-xCl4. Here we verify experimentally the existence of some of these compounds. Indeed, we studied the influence of aliovalent substitution of Zn 2+ and Al 3+ in the two end members. A series of Na1+xZnxAl1-xCl4 (NZAC) samples were mechanochemically synthesized analogously to NAC and NZC. The XRD patterns collected for nominal compositions Na1+xZnxAl1-xCl4 (0 ≤ x ≤ 1) are shown in Figure . At first sight, it may seem that all reflections can be attributed to either NAC or NZC, indicating that no additional phases were formed as the substitution degree (x) varied.