New, potentially green, and efficient synthetic routes for the remediation and/or re-use of perchlorate-based energetic materials have been developed. Four simple organic imidazolium- and phosphonium-based perchlorate salts/ionic liquids have been synthesized by simple, inexpensive, and nonhazardous methods, using ammonium perchlorate as the perchlorate source. By appropriate choice of the cation, perchlorate can be incorporated into an ionic liquid which serves as its own electrolyte for the electrochemical reduction of the perchlorate anion, allowing for the regeneration of the chloride-based parent ionic liquid. The electrochemical degradation of the hazardous perchlorate ion and its conversion to harmless chloride during electrolysis was studied using IR and ³⁵Cl NMR spectroscopies.