In this work, a series of A3-copper corroles bearing different fluoroalkyl, fluoroalkyl, and vinyl substituents at the meso positions are investigated as isolated complexes and their corresponding hybrid systems supported on a pristine graphene sheet (Fig. ). The fluorinated substituents of the studied Cu corroles were selected since they promote the stability of the corrole structure and increase the formal high valent character of the metal center . Furthermore, the nature of the substituents (noted R on Fig. ) was selected to evaluate the effect of the aryl, alkyl, or vinyl skeleton, as well as the rigidity of the corresponding substituent on the stability of non-covalent interactions. Density functional theory (DFT) calculations were performed to gain insights into the main parameters controlling the occurrence of graphene-corrole hybrids