Graphene can be decorated with functional groups on either side of its basal plane, giving rise to a bifunctional nanoscale building block that can undergo face-to-face assembly. We demonstrate that benzoic acid-functionalized graphene (BFG) can act as a structure-directing template in influencing the crystal growth of metal-organic framework (MOF). BFG is also incorporated into MOF as framework linker. Because of the high density of carboxylic groups on benzoic acid-functionalized graphene, an unusual MOF nanowire that grows in the [220] direction was synthesized. The diameter of the nanowire correlates closely with the lateral dimensions of the BFG. The intercalation of graphene in MOF imparts new electrical properties such as photoelectric transport in the otherwise insulating MOF. The results point to the possibility of using functionalized graphene to synthesize a wide range of structural motifs in MOF with adjustable metrics and properties.