Chiral heterocycles occur in many compounds of interest, but their efficient synthesis is challenging. This study concerns the enantioselective and diastereoselective synthesis of densely substituted chiral pyran derivatives. Diastereodivergence of the oxa‐Diels‐Alder reaction is achieved by using either a bifunctional amino‐thiourea or a monofunctional quinine organocatalyst under ball‐milling conditions. Liquid‐assisted grinding proves a highly efficient means of affording pyrans in high yield, with high enantiomeric purities and short reaction times.