The established rates of glycoside hydrolysis reactions were analyzed using free energy relationship plots based on substituent constants that depend on whether the substituent is axial or equatorial. In all cases good correlations were found when assuming either that the transition state had a charged ring-oxygen atom or that it had a charged anomeric carbon atom. The spontaneous hydrolysis of 2,4-dinitrophenyl beta-glycopyranosides and the acidic hydrolysis of methyl beta-D-glycopyranosides were found to give a good correlation, when 100% charge at the ring-oxygen in the transition state of these reactions is assumed. The acidic hydrolysis of methyl alpha-glycopyranosides was found to give good correlations regardless of whether 100% charge at the ring-oxygen or 100% charge at the anomeric carbon was assumed. The findings clearly demonstrate how crucial the stereochemistry of even remote polar substituents is for their electronic effect on chemical reaction.