The family of group IV-VI monochalcogenides has an atomically puckered layered structure, and their atomic bond configuration suggests the possibility for the realization of various polymorphs. Here, we report the synthesis of the first hexagonal polymorph from the family of group IV-VI monochalcogenides, which is conventionally orthorhombic. Recently predicted four-atomic-thick hexagonal GeSe, so-called γ-GeSe, is synthesized and clearly identified by complementary structural characterizations, including elemental analysis, electron diffraction, high-resolution transmission electron microscopy imaging, and polarized Raman spectroscopy.The electrical and optical measurements indicate that synthesized γ-GeSe exhibits high electrical conductivity of 3×10 5 S/m, which is comparable to those of other two-dimensional layered semimetallic crystals. Moreover, γ-GeSe can be directly grown on h-BN substrates, demonstrating a bottom-up approach for constructing vertical van der Waals heterostructures incorporating γ-GeSe. The newly identified crystal symmetry of γ-GeSe warrants further studies on various physical properties of γ-GeSe. ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website. Extra data on the synthesized products, extra EDX mapping data, extra SAED/STEM analysis data along various zone axes, polarized Raman spectra, and extra electronic bandstructure calculations, synthesis and characterizations of vertical γ-GeSe/hBN heterostructures, Raman shift calculations, and γ-GeSe crystallographic information file.