Mg2Sn is a potential thermoelectric (TE) material that can directly convert waste heat into electricity. In this study, Mg2Sn single-crystal ingots are prepared by melting under an Ar atmosphere. The prepared ingots contain Mg vacancies (VMg) as point defects, which results in the formation of two regions: an Mg2Sn single-crystal region without VMg (denoted as the single-crystal region) and a region containing VMg (denoted as the VMg region). The VMg region is embedded in the matrix of the single-crystal region. The interface between the VMg region and the single-crystal region is semi-coherent, which does not prevent electron carrier conduction but does increase phonon scattering. Furthermore, electron carrier concentration depends on the fraction of VMg, reflecting the acceptor characteristics of VMg. The maximum figure of merit zTmax of 1.4(1) × 10−2 is realised for the Mg2Sn single-crystal ingot by introducing VMg. These results demonstrate that the TE properties of Mg2Sn can be optimised via point-defect engineering.