Picryl chloride reacts rapidly with methoxide ion in methanol to form a σ-complex containing methoxide ion attached to the C-3 position of the picryl chloride. Thermodynamic and kinetic parameters characterizing this reaction are presented and compared with corresponding parameters for the analogous reaction of methoxide ion and 2,4,6-trinitroanisole in methanol. Details concerning the much slower formation of the σ-complex containing methoxide ion added to the C-1 position of picryl chloride are also presented.