We describe the spectroscopic characterization of the anions produced by low-energy electron attachment to neutral clusters of 2-chloroacrylonitrile (CAN). The photoelectron spectrum of the CAN(-) anion is markedly similar to that of the ion-molecule complex, Cl-.CAN, implying that the excess charge in CAN(-) is localized on the chlorine atom. Ab initio calculations support this inference, indicating that upon electron attachment CAN(-) rearranges to a novel distonic ion-radical complex, Cl-.H2C=CCN. The photoabsorption spectrum of the anion is consistent with a charge transfer transition to an excited state, Cl.[H2C=CCN](-)*. This chromophore dominates the photofragmentation chemistry of CAN(-), with the dominant photofragments at all wavelengths being Cl- (presumably formed by reverse charge transfer relaxation of the excited state) and [H2C=CCN](-). The propensity of neutral clusters of CAN to polymerize upon electron attachment is readily explicable in view of the proposed ion-radical structure of CAN(-).