Over the past five years, maleimide scaffolds have gained considerable attention in organic synthesis for their role in forming cyclized molecules through annulation and C–H activation. As versatile and reactive coupling agents, maleimides have enabled the efficient synthesis of various cyclized products, including annulation, benzannulation, cycloaddition, and spirocyclization, with applications in medicinal chemistry, drug discovery, and materials science. Despite the extensive study of maleimide chemistry, certain reactions—such as cycloaddition-based annulation, photoannulation, and electrochemical transformations—remain underexplored despite their promising potential in the pharmaceutical and chemical industries. Recent advancements, such as photocatalysis and electrochemical methods, have expanded the utility of maleimides, providing more sustainable and selective approaches for synthesizing complex molecules. This review compiles research published between 2019 and 2024, highlighting the substrate scope, reaction diversity, and industrial relevance of maleimide-based annulation strategies. Additionally, we discuss emerging trends and future directions in maleimide chemistry, exploring opportunities for novel reaction pathways and broader applications in synthetic biology and materials science.