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Bicyclo[1.1.1]pentane (BCP) serves as an increasingly indispensable arene bioisostere in modern medicinal chemistry. In this cover feature, we disclose a visible‐light‐induced four‐component reaction (4CR) that enables the convergent synthesis of diverse disubstituted BCP derivatives in a single pot. Notably, this protocol leverages an electron donor–acceptor (EDA) complex to initiate the transformation under catalyst‐free conditions, eliminating the need for both transition metals and external photoredox catalysts. With its good functional‐group tolerance and scalability, this methodology offers a practical toolbox for pharmaceutical discovery. More details are discussed in the article by Xu et al . on pages 3813—3822.
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