A mild, synthetically straightforward and selective PPh 3 ‐promoted remote (4 + 3) cycloaddition reactions of pyrrolidinone‐based Morita–Baylis–Hillman carbonates with α,β‐unsaturated imines have been first established. This reaction enables the synthesis of a diverse range of synthetically valuable, highly substituted pyrrolo[2,3‐ b ]azepines bearing three tertiary chiral centers in good yields (up to 87%) with excellent chemo‐, regio‐, and diastereoselectivities (all cases >25:1 dr). In addition, the synthetic utility of this method was further demonstrated by scale‐up reactions and synthetic transformations of the product. Additionally, molecular docking studies have revealed that the novel fuzed bicyclic privileged structures, which incorporate azepine and pyrrolone motifs, possess potential anticancer activity.