Three-dimensional graphene structures have attracted a great interest these last years. The combination of well-known graphene properties and a large specific surface area developed by their intrinsic porosity is especially interesting for challenging applications such as energy storage and conversion or catalysis. This work is focused on the elaboration of graphene foams by pyrolysis of sodium ethoxide. Whereas the literature mentions the possible elaboration of graphene foams by combustion of sodium ethoxide synthesized by a quite heavy solvothermal-based process, we propose here a thermal treatment consisting in a pyrolysis under a nitrogen flow. Using commercial sodium ethoxide, we show that this treatment leads to the preparation of graphene foams with great structural quality and high specific surface area. This original result is supported by a compared characterization of solvothermal and commercial sodium ethoxide and the proposition of a formation mechanism of the three-dimensional graphene network during the pyrolysis is proposed. This new graphene foam elaboration route is extremely interesting in order to consider a large-scale fabrication of such materials.