Multilayer structures comprising a covalent organic framework (COF) film in contact with a polyaromatic carbon (PAC) film. The multilayer structures can be made by combining precursor compounds in the presence of a PAC film. The PAC film can be for example, a single layer graphene film. The multilayer structures can be used in a variety of applications such as solar cells, flexible displays, lighting devices, RFID tags, sensors, photoreceptors, batteries, capacitors, gas-storage devices, and gas-separation devices.