AbstractTwo-dimensional piezotronics will benefit from the emergence of new crystals featuring high piezoelectric coefficients. Gallium phosphate (GaPO₄) is an archetypal piezoelectric material, which does not naturally crystallise in a stratified structure and hence cannot be exfoliated using conventional methods. Here, we report a low-temperature liquid metal-based two-dimensional printing and synthesis strategy to achieve this goal. We exfoliate and surface print the interfacial oxide layer of liquid gallium, followed by a vapour phase reaction. The method offers access to large-area, wide bandgap two-dimensional (2D) GaPO₄ nanosheets of unit cell thickness, while featuring lateral dimensions reaching centimetres. The unit cell thick nanosheets present a large effective out-of-plane piezoelectric coefficient of 7.5 ± 0.8 pm V⁻¹. The developed printing process is also suitable for the synthesis of free standing GaPO₄ nanosheets. The low temperature synthesis method is compatible with a variety of electronic device fabrication procedures, providing a route for the development of future 2D piezoelectric materials.