Metalloporphyrins are well known for their electron-transfer roles in many natural redox systems. In addition, several metalloporphyrins and related tetrapyrrole macrocycles complexed with various core metals have been shown to catalyze the reductive dechlorination of certain organic compounds, thus demonstrating the potential for using naturally occurring metalloporphyrins to attenuate toxic and persistent chlorinated organic pollutants in the environment. However, despite the great interest in reductive dechlorination reactions and the wide variety of natural and synthetic porphyrins currently available, only soluble porphyrins, which comprise a small fraction of this particular family of organic macrocycles, have been used as electron-transfer shuttles in these reactions. Results from the present study clearly demonstrate that metalloporphyrin solubility is a key factor in their ability to catalyze the reductive dechlorination of tetrachloroethylene and its daughter compounds. Additionally, we show that certain insoluble and nonreactive metalloporphyrins can be activated as catalysts merely by changing solution conditions to bring about their dissolution. Furthermore, once a metalloporphyrin is fully dissolved and activated, tetrachloroethylene transformation proceeds rapidly, giving nonchlorinated and less toxic alkenes as the major reaction products. Results from the present study suggest that if the right environmental conditions exist or can be created, specific metalloporphyrins may provide a solution for cleaning up sites that are contaminated with chlorinated organic pollutants.