Substituted chloromethyl radicals and anions are potential intermediates in the reduction of substituted chlorinated methanes (CHxCl3-xL,with L- = F-, OH-, SH-, NO3-, HCO3- and x = 0-3). Thermochemical properties, DeltaH(f)(0)(298.15 K), Sdegrees(298.15 K, 1 bar), and DeltaG(S)(298.15 K, 1 bar), were calculated by using ab initio electronic structure methods for the substituted chloromethyl radicals and anions: CHyCl2-yL. and CHyCl2-yL-, for y = 0-2. In addition, thermochemical properties were calculated for the aldehyde, ClHCO, and the gemchlorchydrin anions, CCl3O-, CHCl2O-, and CH2ClO-. The thermochemical properties of these additional compounds were calculated because the nitrate-substituted compounds, CHyCl2-y(NO3)(.) and CHyCl2-y(NO3)(-), were not stable, with all levels of ab initio theory leading to highly dissociated complexes. On the basis of these thermochemical estimates, the overall reaction energetics (in the gas phase and aqueous phase) for several mechanisms of the first electron reduction of the substituted chlorinatedmethanes were predicted. In almost all of the cases, the thermodynamically most favorable pathway resulted in loss of Cl-. The exception was for the reduction of the nitrate-substituted chlorinated methanes CHCl3-x(NO3). On reduction, these compounds were shown to readily decompose into a Cl- anion, NO2. gas, and an aldehyde. In addition, the results of this study suggest that a higher degree of chlorination corresponds to a more favorable reduction. Relative to the nonsubstituted chlorinated methanes, the thermodynamic results suggest the CHCl3-xF, CHxCl3-xOH, and CHxCl3-x(HCO3) compounds are moderately more difficult to reduce, the CHxCl3-xSH compounds are moderately less difficult to reduce, and the CHxCl3-x(NO3) compounds are substantially more favorable to reduce. These results demonstrate that ab initio electronic structure methods can be used to calculate the reduction potentials of organic compounds to help identify the potentially important environmental degradation reactions.