Transition metal-catalyzed reactions have emerged as powerful tools for constructing tailored polycyclic aromatic hydrocarbon (PAH) architectures, offering precise control over the formation of carbon-carbon bonds and enabling the synthesis of complex PAH structures with specific shapes, sizes, and functionalities. Palladium, nickel, copper, and ruthenium catalysts facilitate C–C coupling, C–H activation, and annulation processes, allowing for the controlled assembly of extended π-conjugated systems. The versatility of these catalysts enables the incorporation of heteroatoms and functional groups, further expanding the diversity of accessible PAH architectures. Computational studies using density functional theory provide insights into transition state stabilization, ligand effects, and electronic structure modulation, aiding in the rational design of efficient PAH synthesis strategies. Functionalized PAHs synthesized via transition metal catalysis find extensive applications in organic electronics, photovoltaics, energy storage, and bioimaging due to their tunable electronic properties, high charge carrier mobility, and excellent thermal stability. However, challenges remain in terms of reaction scalability, catalyst stability, and the integration of computational predictions with experimental outcomes. Future research should focus on developing sustainable catalytic systems, improving reaction efficiency, and expanding the scope of PAH-based materials for emerging applications in nanotechnology and molecular electronics. By addressing these challenges, transition metal-catalyzed PAH synthesis will continue to drive innovation in the development of advanced functional materials and next-generation electronic devices.