Enhancing the performance of thermoelectric materials is demanded to develop strategies for introducing multidimensional microstructures into materials to induce full-scale phonon scattering while ensuring electrical transport performance. Herein, a previously unreported rhombohedral h-SnTe (R3̄m) has been achieved in the nanoscale dimension by the electron beam irradiation of β-SnTe (Fm3̄m) materials. The h-SnTe structure contains interlayer van der Waals gaps and exhibits metallic behavior evaluated by density-functional theory calculations, which coherently appears in the narrow-band semiconductor β-SnTe matrix. Our results provide a strategy for modifying the properties of SnTe-based thermoelectric materials and designing nanostructured chalcogenide heterostructures via electron beam irradiation.