In this work, we aimed to use the chiral perturbation of a stereogenic P-atom (within a phosphetene ring) to chirally perturb linearly fused PAHs. Hence, phosphetene is a 4-membered P-ring that, despite being barely investigated, has started to be used in the context of molecular materials and optoelectronics. We describe the synthesis of four new PAHs fused to a phosphetene ring. The impact of both the polyaromatic platform and the P-ring on the structure, as well as the optical and redox properties of the compounds are investigated experimentally and using theoretical methods. Finally, we show that the stereogenic P-ring acts as an efficient chiral perturbator to induce circularly polarized luminescence of the polyaromatic system with glum of 10 -3 . To prepare phosphetenes 1-4, Doxsee's one-pot methodology was used starting from the corresponding alkynes (Scheme 1). The phosphetenes having trivalent P-centres ( 31 P NMR: -17 ppm) were oxidized in situ to form the corresponding phosphetene oxides ( 31 P NMR: +20 ppm), which can easily be handled in air. All compounds were synthesized in moderate yields (31-46%) and were fully characterized by multinuclear NMR, mass spectrometry and their structures were unequivocally confirmed by single crystal X-ray diffraction (Scheme 1). The unit cells are all composed by a racemic mixture of the two enantiomers, with the P atom as a stereogenic centre. In all these derivatives, the P-ring is a distorted square (Table ) with usual bond distances and angles for phosphetenes. The lateral aryl groups are twisted from the plane of the P-ring. Such a structural property will have an impact on the conjugation in the systems (vide infra). No intermolecular interactions were observed in the packing.