Graphene nanomaterials have great potential applications in treating wastewater containing pharmaceutical residues due to their extraordinary physicochemical and adsorption properties. Despite being present in minute amounts in the aquatic environment, pharmaceutical residues can cause various health and environmental risks owing to their non-biodegradability, bioaccumulative and toxicity features. Hence, it is extremely vital to control the concentration of pharmaceutical residues in water resources. Notably, three-dimensional (3D) graphene structures have emerged as innovative adsorbents with fortified adsorption properties such as super-large theoretical surface area, abundant functional groups, and the capability to preserve the intrinsic properties of nanomaterials at a macroscopic level. In this chapter, the classification and main sources of pharmaceutical pollution are discussed. Thereafter, the principles and advantages of adsorption for pharmaceutical removal are covered. This chapter further evaluates the performance of primary 3D graphene structures, namely graphene aerogel, hydrogel, and beads, in relation to pharmaceutical adsorption. The synthesis methods and adsorption mechanisms of pharmaceutical residues by 3D graphene structures are assayed. Lastly, the challenges and outlook of 3D graphene structures in pharmaceutical adsorption are presented.