Solvolysis reactions, in which the solvent itself acts as the nucleophile, remain one of the most informative mechanistic probes in physical organic chemistry. This article examines how the class of an alcoholic solvent — primary (e.g., methanol, ethanol) versus tertiary (e.g., tert-butanol) — governs the rate of solvolysis of alkyl halides and related electrophiles. Using the Grunwald–Winstein linear free-energy relationship (Grunwald and Winstein, 1948) and its later two-parameter extension incorporating solvent nucleophilicity, the kinetic consequences of solvent polarity, dielectric constant, hydrogen-bond-donating ability and steric bulk are analysed. Primary alcohols combine moderate-to-high ionizing power with appreciable nucleophilicity and low steric hindrance, providing significant nucleophilic solvent assistance and comparatively fast solvolysis. Tertiary alcohols, in contrast, are poor nucleophiles because of steric crowding around the oxygen atom and possess markedly lower dielectric constants, which together depress both the ionizing and nucleophilic components of the rate law. Representative kinetic trends, a Grunwald–Winstein correlation, and Arrhenius data are used to illustrate these effects, and the mechanistic implications for the SN1–SN2 continuum are discussed.