Biomimetic fabrication has long been considered a short cut to the rational design and production of artificial materials or devices that possess fascinating properties, just like natural creatures. Considering the fact that graphene exhibits a lot of exceptional properties in a wide range of scientific fields, biomimetic fabrication of graphene multiscale structures, denoted as biomimetic graphene, is of great interest in both fundamental research and industrial applications. Especially, the combination of graphene with biomimetic structures would realize structural and functional integrity, and thus bring a new opportunity of developing novel graphene-based devices with remarkable performance. In this feature article, we highlight the recent advances in biomimetic graphene films and their structure-defined properties. Functionalized graphene films with multiscale structures inspired from a wide range of biomaterials including rose petals, butterfly wings, nacre and honeycomb have been collected and presented. Moreover, both current challenges and future perspectives of biomimetic graphene are discussed. Although research of the so-called “biomimetic graphene” is still at an early stage, it might become a “hot topic” in the near future.