In contrast to observations with carbohydrates, experiments with 4‐alkoxy‐substituted acetals indicate that an alkoxy group can accelerate acetal hydrolysis by up to 20‐fold compared to substrates without an alkoxy group. The acceleration of ionization in more flexible acetals can be up to 200‐fold when compensated for inductive effects. Making an approach: In contrast to observations with carbohydrates, alkoxy groups can accelerate acetal hydrolysis even though they are inductively electron withdrawing. The alkoxy group must be able to approach the acetal carbon atom without developing too much strain. The data are most consistent with the alkoxy group stabilizing the developing positive charge by electrostatic stabilization, not formation of a new covalent bond.