The enantioenriched azaarene derivatives have garnered significant interest in pharmaceutical and synthetic chemistry, prompting the development of efficient catalytic methodologies. Recent advancements have leveraged the high reactivity of radicals in conjunction with the hydrogen-bonding interactions characteristic of azaarenes. Notably, the integration of visible light-driven photocatalysis with chiral Brønsted acid catalysis has emerged as a powerful platform for synthesizing these valuable compounds. This chapter presents an overview of the state-of-the-art strategies established for the enantioselective synthesis of diverse and complex azaarene derivatives, emphasizing sustainable and mild reaction conditions. The discussion is structured according to the stereocenter positions within azaarenes – specifically, α-, β-, γ-, and various other positions. Ultimately, this chapter aims to elucidate current achievements while identifying existing challenges, thereby inspiring chemists to explore novel or more efficient approaches for accessing enantiomerically pure azaarene derivatives, whether their structures are known or yet to be discovered, thus fostering rapid advancements within the pharmaceutical sector.