A simple hydrophobic-affinity-derived assembly approach to pack graphene sheets into a nanoporous foam structure has been developed. Nanoporous graphene foams with the highest pore volume and large surface area are obtained. The pore diameter of the graphene foams can be finely adjusted from the mesopore to the macropore range by employing spherical templates with different sizes. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.