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Abstract AMX compounds with the ZrBeSi structure tolerate a vacancy concentration of up to 50 % on theM ‐site in the planarMX ‐layers. Here, we investigate the impact of vacancies on the thermal and electronic properties across the full EuCu1−x Zn0.5x Sb solid solution. The transition from a fully‐occupied honeycomb layer (EuCuSb) to one with a quarter of the atoms missing (EuZn0.5Sb) leads to non‐linear bond expansion in the honeycomb layer, increasing atomic displacement parameters on theM and Sb‐sites, and significant lattice softening. This, combined with a rapid increase in point defect scattering, causes the lattice thermal conductivity to decrease from 3 to 0.5 W mK−1at 300 K. The effect of vacancies on the electronic properties is more nuanced; we see a small increase in effective mass, large increase in band gap, and decrease in carrier concentration. Ultimately, the maximumzT increases from 0.09 to 0.7 as we go from EuCuSb to EuZn0.5Sb.