Abstract1,3‐Dipolar cycloaddition through in situ generation of azomethine ylide provides a straightforward and critically important sustainable approach for access to diverse pyrrolidine chemical space. Herein, we developed a metal‐free AcOH‐activated 1,3‐dipolar cycloaddition protocol that permits the synthesis of uncommon pyrrolidine cycloadducts with excellent diastereoselectivity. The challenging substrates of 3‐formylchromone, glycine ester.HCl and arylidene dipolarophile were reacted in the presence of AcONa, which played a dual role as a base and AcOH source, to deliver firstly endo‐cycloadduct. Under prolonged reaction time at room temperature or heating; the endo‐adduct underwent diastereodivergent via a sequence of retro‐cycloaddition, stereomutation of the generated syn‐dipole into anti‐dipole and recycloaddition; to furnish the scarcely known exo′‐cycloadduct with high diastereodivergency. The reaction worked well with a broad range of substrates and the stereochemistry of the obtained cycloadducts was determined without ambiguity using NMR‐ and X‐ray analysis. Experimental and theoretical DFT calculation studies were performed to support the proposed reaction mechanism and elucidate the key role of AcOH in the process which seems more beneficial than other transition metal‐catalyzed processes.