Polycyclic aromatic hydrocarbons (PAHs) are highly appealing functional materials in the field of molecular electronics. In particular, molecular engineering of these derivatives by using organic chemistry is a powerful method to tune their properties from the point of view of the band gap and supramolecular assemblies. Another way to achieve such control is to take advantage of the specific reactivity of heteroatoms placed within the sp²‐carbon framework. This strategy has been successfully applied to nitrogen, sulfur and boron. In this review, examples of phosphorus‐containing PAHs and the effect of the phosphorus environment on the electronic properties from both experimental and theoretical points of view are discussed.