(Chemical Equation Presented) Density functional theory electronic structure calculations of the homolytic/heterolytic aniomesolytic C-O fragmentations in the gas phase of a series of radical anions of substituted-phenyl benzyl ethers and substituted-benzyl phenyl ethers have been carried out. Along the series, the electron-withdrawing strength of the substituents increases. An intramolecular electron transfer from the π system to the σ* molecular orbital of the scissile C-O bond is required to produce the fragmentation. As the electron-withdrawing strength of the substituents increases, the transition-state structures appear later with higher potential energy and Gibbs free energy barriers. The homolytic mesolytic cleavages are always thermodynamically favored versus the corresponding heterolytic mesolytic ones. The heterolytic mesolytic fragmentations in radical anions containing only weak electron-withdrawing groups are faster than the corresponding homolytic mesolytic ones. Conversely, in radical anions supporting strong electron-withdrawing groups the homolytic mesolytic fragmentations are faster in terms of potential energy barriers. However, the entropic contribution makes it comparable the homolytic and the heterolytic Gibbs free energy barriers in this case. The main factors that determine the relative rates of those kind of aniomesolytic cleavages are discussed.