Polycyclic Aromatic Hydrocarbons (PAHs) with planar, twisted and negatively curved topologies were obtained from polycyclic phospholes using pericyclic reactions. Deviation from planarity is due to steric interactions between the PAH core and the ester substituents. These structural effects on the optical and redox properties were studied and rationalized through DFT calculations. This synthetic approach thus allows the preparation of topologically diverse PAHs allowing fine-tuning their electronic properties, with potential applications in organic electronics.