The photoelectron-induced dissociation of CH3Cl adsorbed on top of a multilayer deposit ejects methyl radicals into the gas phase. The kinetic energies of these methyls vary with the identity of the underlying multilayer (H2O, hexane, CH3Cl), from 0.44 to 0.7 eV at the peak, and are much higher than seen for the gas-phase dissociative electron attachment to this molecule. The additional energy is understood in terms of the effects of the "prompt" solvation (< 40 fs) on the anionic repulsive curve and suggests a powerful approach to probing it.