The study reported here concerns the preparation of a novel graphene-diaminotriazine (G-DAT) nanocomposite hydrogel for application in the drug delivery field. The hybrid nature of this material is founded on two key elements: the presence of the DAT backbone induced the formation of hydrophobic regions that allowed efficient loading of a series of drugs of increasing hydrophobicity (Metronidazole, Benzocaine, Ibuprofen, Naproxen and Imipramine), while simultaneously endowing swelling-induced pH-responsiveness to the hydrogel. Additionally, the incorporation of graphene was found to interfere with these hydrophobic domains through favourable non-covalent interactions, thus leading to the partial disruption of these aggregates. As a consequence, graphene facilitated and enhanced the release of model hydrophobic drug Imipramine in a synergistic manner with the pH trigger, and increased the swelling capacities and improved mechanical performance. This hybrid hydrogel can therefore be envisaged as a proof-of-concept system for the release of hydrophobic compounds in the field of drug delivery.