The alpha-effect, an enhanced reactivity of nucleophiles with a lone-pair adjacent to the reaction center, has been studied in solution for several decades. The gas-phase alpha-effect has recently been documented in studies of S(N)2 reactions as well as in competing reactions for both bare and microhydrated anions. In the present work we extend our studies of the significance of microsolvation on the alpha-effect, employing methanol as the solvent, in the expectation that the greater stability of the methanol cluster relative to the water cluster will lower the reactivity and thereby allow studies over a wider efficiency range. We compare the gas-phase reactivity of the microsolvated alpha-nucleophile HOO-(CH3OH) to that of microsolvated normal alkoxy nucleophiles, RO-(CH3OH) in reactions with CH3Cl and CH3Br. The results reveal enhanced reactivity of HOO-(CH3OH) toward both methyl halides relative to the normal nucleophiles, and clearly demonstrate the presence of an alpha-effect for the microsolvated alpha-nucleophile. The highly exothermic reactions with methyl bromide result in a smaller Bronsted beta(nuc) value than observed for methyl chloride, and the alpha-effect in turn influences the reactions with methyl chloride more than with methyl bromide. Computational investigations reveal that reactions with methyl bromide proceed through earlier transition states with less advanced bond formation compared to the related reactions of methyl chloride. In addition, solvent interactions for HOO- are quite different from those with the normal nucleophiles at the transition state, indicating that differential solvation may well contribute to the alpha-effect. The greater thermodynamic and kinetic stability of the anion-methanol clusters relative to the anion-water clusters accounts well for the differences in the influence of solvation with the two protic polar solvents.