Polycyclic aromatic hydrocarbons (PAHs) are important organic building blocks for optoelectronic applications. Among the various molecular engineering strategies (pi-extension, edge structure modification, exocyclic functionalization), this review will focus on the insertion of heavy group 14 elements (Si, Ge and Sn) into the polyaromatic backbone. The main synthetic approaches toward these compounds will be discussed. Their optical and redox properties will be described with a particular attention of the specific effect of the heteroatom. Finally, there insertion into optoelectronic devices will be highlighted.