Novel Polymorph of GaSe

2D GaSe is a semiconductor belonging to the group of post-transition metal chalcogenides with great potential for advanced optoelectronic applications. The weak interlayer interaction in multilayer 2D materials allows the formation of several polymorphs. Here, the first structural observation of a new GaSe polymorph is reported, characterized by a distinct atomic configuration with a centrosymmetric monolayer (D_3d point group). The atomic structure of this new GaSe polymorph is determined by aberration-corrected scanning transmission electron microscopy. Density-functional theory calculations verify the structural stability of this polymorph. Furthermore, the band structure and Raman intensities are calculated, predicting slight differences to the currently known polymorphs. In addition, the occurrence of layer rotations, interlayer relative orientations, as well as translation shear faults is discussed. The experimental confirmation of the new GaSe polymorph indicates the importance of investigating changes in the crystal structure, which can further impact the properties of this family of compounds.