A synthetic route to planar P-modified polycylic aromatic hydrocarbons (PAHs) is described. The presence of a reactive sigma(3),lambda(3)-P moiety within the sp(2)-carbon scaffold allows the preparation of a new family of PAHs displaying tunable optical and redox properties. Their frontier molecular orbitals (MOs) are derived from the corresponding phosphole MOs and show extended conjugation with the entire pi framework. The coordination ability of the P center allows the coordination-driven assembly of two molecular PAHs onto a Au-I ion.