The assembly of nano-building blocks into a desired architecture is a challenging subject in the current materials science. It is critical to direct the macroscopic-scale as well as molecular-scale arrangements of various functional nanomaterials. Particularly, the assembly of graphene oxide based polymer composites into film, fiber, gel or micropatterned material may provide versatile opportunities for applications in nanoelectronics, energy devices, sensors, bioscaffolds, etc. Here I present a versatile and robust functionalization method for graphene oxide with polymers and facile directed-assembly method to produce cellular graphene oxide based polymer composites scaffolds with tunable morphologies. Graphene Oxide based polymer composites were decorated with various polymers covalently or noncovalently through charge-charge interaction or surface-initiated atom transfer radical polymerization (ATRP). The self-organization of aqueous droplets upon a volatile solution, generally known as a ‘breath figure’, has been applied to the organic solution containing both polymer and graphene oxide as solutes and yielded macroporous polymer/graphene oxide nanocomposite films. Upon the calcination of the polymer matrices, the resultant highly entangled graphene oxide scaffolds maintained the macroporous morphology. In this work, their electric conductivity, lithium ion battery anodes and supercapacitor performance have been explored to elucidate potential applications for nanoelectronics and energy storage materials.