The reaction of tetranitromethane (4NM) with a series of alcohols [CH3OH, C2H5OH, «-C3H7OH, /-C3H7OH, iez-z-C4H9OH, CH3OCH2CH2OH, HOCH2CH2OH, C(CH2OH)4, N-acetylserinamide, CF3CH2OH] and inorganic ions [HO™, I™, CN™, SCN", NOr, N3™, S2032™] has been investigated. Both quantitative product analysis (where allowed) and determination of rate equations were carried out as were esr spectral studies for selected reactions [4NM with CH3OH, C2H5OH, CF3CH2OH, rer/-C4H9OH, CH3OCH2CH2OH, and Ar-acetylserinamide].In the reaction of C2H5OH, «-C3H7OH, /-C3H7OH, fe/T-C4H9OH, CH3OCH2CH2OH, and HOCH2CH2OH with 4NM the following rate law pertained: kab!d = &oh[OH™] + fci[RO~] + Ár2 [ROH][RO™] (eq a). For reaction of 4NM with CH3OH and C(CH2OH)4 the term ¿2[ROH][RO™] was not discernible while kuhid was found to be independent of [CF3CH2OH + CF3CH20~]. Product analysis establishes that trinitromethane anion (3NM) but not nitrite ion, plus alkyl nitrate, arise from the reaction paths associated with both ki and k2 (eq a) for all reactive alcohols except /erf-butyl alcohol. For the ?ezt-C4H9OH 60-70 % of starting 4NM appears as X 4 N02™. Spectral (esr) studies did not detect stable free radical intermediates in the reactions of the alcohols with 4NM. The reaction of 4NM with M-acetylserinamide (NASA) appears highly complex, and was not comparable to the other alcohols; esr evidence indicates considerable radical formation in the reaction of NASA with 4NM. The rate constants ki and k2 (eq a) were found to be linear functions of the pKd of the alcohol involved. Of the various mechanisms considered the one suggested as possibly the most reasonable involves the reaction of RO™ with 4NM to provide an anion-cation radical pair species followed by spontaneous electron transfer (ki) or hydrogen atom abstraction from ROH (ki) to yield R0N02 as product. To account for altered products in the case of tert-CiH9OH it has been suggested that RO™ attack at an oxygen of 4NM yields a cation-anion pair which then undergoes spontaneous electron transfer (ki) or hydrogen atom abstraction (ki) from ?m-C4H9OH. Reaction of p-cresol with 4NM under conditions of [4NM] » [phenol + phenolate] yields only 10-20% o-nitrocresol which is in accord with earlier results obtained under conditions of [phenol + phenolate] )$> 4NM. The reaction of the inorganic ions with 4NM were found to be first order in 4NM and first order in anion (Aza-)• For the inorganic anions (excluding I™ + S2032™) a plot of log kt, -vs. pKd of the conjugate acids of the anion is linear and of slope 0.27 ± 0.02. A mechanism involving anion attack on a nitrogen of 4NM to provide 3NM plus nitrated anion is suggested for these anions.The small value of ß suggests little bond formation in the transition state and the correlation of log k\ -with Edward's Hn rather than £" values is in accord with initial anion attack upon sp2 hybridized nitrogen. For I™ and S2032™, reduction of 4NM is suggested as a plausible mechanism; in the case of I™, I2 is formed. These species exhibit a positive deviation (ca. ...