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The influence of stereochemistry on the mechanochemistry rate is studied using a new mechanophore based on a benzopinacol (BP) skeleton. Two sets of BP diastereomers, the meso R,S and the R,R/S,S were isolated, incorporated into the center of a poly(methyl acrylate), and their mechanical activation rate was measured in solution. Under mechanical stress, the central C−C bond in BP is cleaved, providing two independent benzophenone molecules with higher UV‐absorption coefficient at 254 nm. Monitoring the reaction rate spectroscopically indicates that the chiral R,R/S,S enantiomers react ~1.4 fold faster compared to the meso R,S diastereomer. In‐silico modeling indicates that a hydrogen bond between the syn hydroxyls in the R,R diastereomer becomes shorter with stress, reducing the maximal force required for C−C bond scission, while this bond is inexistent in the meso diastereomer, as the hydroxyl are anti to each other. Our results indicate that in polymer where free rotation around bonds is possible, non‐covalent interactions between backbone substituents, which are affected by relative stereochemistry, can play a fundamental role in the mechanochemical stability of the polymer. [ABSTRACT FROM AUTHOR]