Inspired by the amphiphilicity of graphene oxide (GO), the surface of water is used as a template for the assembly of a GO film. Methacrylate-functionalized GO sheets can be cross-linked instantaneously at the water–air interface to form a highly wrinkled membrane spreading over an extended area. The multiple covalent linkages amongst the GO sheets enhances the in-plane stiffness of the film compared to noncovalently bonded GO films. The highly convoluted GO membrane can be used in two applications: the promoting of spontaneous stem-cell differentiation towards bone cell lineage without any chemical inducers, and for supercapacitor electrodes. Due to reduced van der Waals restacking, capacitance values up to 211 F g−1 can be obtained. The scalable and inexpensive nature of this assembly route enables the engineering of membranes for applications in regenerative medicine and energy-storage devices where secondary structures like nanotopography and porosity are important performance enhancers.