The detoxification process mediated by carboxylic acids (CAs) has received considerable spotlights since CAs are clean reagent and ubiquitous in the natural environments and effluents. Here, we present an exhaustive review on surface-bound/dissolved metals-catalyzed Cr(VI) reduction by CM and CM-mediated Cr(VI) reduction by many highly/poorly reductive reagents. The overall mechanisms of Cr(VI) reduction are mainly associated with the coordination of CAs with surface-bound/dissolved metals or Cr(VI,V,IV) species and the electron donating abilities of CM. Additionally, the general decays of intermediate Cr(V,IV) complexes are clearly emerged in the Cr(VI) reduction processes. The performance of various reaction systems for Cr(VI) reduction that is greatly dependent on the operation parameters, including solution pH, reagent concentration, temperature, coexisting ions and gas atmosphere, are also critically commented. From the study survey presented herein, CM-mediated Cr(VI) reduction processes exhibit good potential for remediation of various Cr(VI)-contaminated waters/sites. However, there is still a need to address the remained bottle-necks and challenges for the remediation of Cr(VI) mediated by CM in the related natural attenuation cases and the treatment of industrial effluents. Overall, the present review offers the comprehensive understanding of the Cr(VI) reduction mediated by CAs and provide the engineering community with the guidelines for Cr(VI) remediation in the real-world applications.