Heteroatom-embedded polycyclic aromatic compounds (hetero-PACs) are a class of organic compounds contributing to a variety of research fields such as materials science, chemical biology and so on. For applications using hetero-PACs, efficient preparation of hetero-PACs is essential. In particular, reactions transforming unfunctionalized aromatic compounds to hetero-PACs using appropriate heteroatom-containing aromatic compounds (π-extending agents) represent the most ideal way to prepare hetero-PACs. In this review, such heteroatom-embedding annulative π-extension (hetero-APEX) reactions including their reaction mechanisms and scope of substrates are described.