Planar and non-planar polycyclic aromatic hydrocarbons (PAHs) may be considered as defined molecular fragments of graphitic carbon allotropes. With the advent of graphene, PAHs have received renewed scientific interest as highly attractive objects for experimental and theoretical studies. Furthermore, PAHs are due to their extended π-conjugation particularly interesting as functional materials for applications in organic electronics. The optoelectronic and materials properties of these appealing π-systems can be fine-tuned by either peripheral substitution or more efficiently by introduction of various heteroatoms directly into their sp2-carbon skeletons. In this talk, our ongoing research efforts towards the synthesis, study, and application of functional π-conjugated architectures based on PAHs with selectively incorporated nitrogen, phosphorus, and other heteroatoms will be presented. Furthermore, the impact of the heteroatom on fundamental characteristics of the surrounding π-system will be discussed and future research directions briefly outlined.