Ferroelectricity in ultrathin two-dimensional (2D) materials has attracted broad interest due to potential applications in nonvolatile memory, nanoelectronics and optoelectronics. However, ferroelectricity is barely explored in materials with native centro or mirror symmetry, especially in the 2D limit. Here, we report the first experimental realization of room-temperature ferroelectricity in van der Waals layered GaSe down to monolayer with mirror symmetric structures, which exhibits strong intercorrelated out-of-plane and in-plane electric polarization. The origin of ferroelectricity in GaSe comes from intralayer sliding of the Se atomic sublayers, which breaks the local structural mirror symmetry and forms dipole moment alignment. Ferroelectric switching is demonstrated in nano devices fabricated with GaSe nanoflakes, which exhibit exotic nonvolatile memory behavior with a high channel current on/off ratio. Our work reveals that intralayer sliding is a new approach to generate ferroelectricity within mirror symmetric monolayer, and offers great opportunity for novel nonvolatile memory devices and optoelectronics applications.

Conventional two‐dimensional electron gas (2DEG) typically occurs at the interface of semiconductor heterostructures and noble metal surfaces, but it is scarcely observed in individual 2D semiconductors. In this study, few‐layer gallium selenide (GaSe) grown on highly ordered pyrolytic graphite (HOPG) is demonstrated using scanning tunneling microscopy and spectroscopy (STM/STS), revealing that the coexistence of quantum well states (QWS) and 2DEG. The QWS are located in the valence bands and exhibit a peak feature, with the number of quantum wells being equal to the number of atomic layers. Meanwhile, the 2DEG is located in the conduction bands and exhibits a standing‐wave feature. Additionally, monolayer GaSe/HOPG heterostructures with different stacking angles (0°, 33°, 8°) form distinct moiré patterns that arise from lattice mismatch and angular rotation between adjacent atomic layers in 2D materials, which effectively modulate the electron effective mass, charge redistribution, and band gap of GaSe. Overall, this work reveals a paradigm of band engineering based on layer numbers and moiré patterns that can modulate the electronic properties of 2D materials.