Despite their diverse application profile, aromatic organochlorides such as 2,4,6-trichlorophenol (TP) are widely renowned for creating a negative toll on the balance of the ecosystem. Strict regulatory regimes are required to limit exposure to such organic pollutants. By deployment of a straightforward detection scheme, electrochemical sensing technology offers a competitive edge over the other techniques and practices available for pollutant monitoring.Here, we present a streamlined hydrothermal approach for synthesizing copper−manganese layered double hydroxide (CuMn-LDH) rods to be employed as electrocatalysts for detecting TP in various media. With a focused intention to leverage the full potential of the prepared CuMn-LDHs, the interlamellar region is configured using a series of intercalants. Further, a thorough comparative analysis of their structures, morphologies, and electrochemical performance is accomplished using various analytical techniques. The electrocatalytic oxidation ability of the CuMn-LDH toward TP molecules is markedly altered by incorporating various anions into the gallery region. The dynamic attributes of the developed sensor, such as a wide linear response (0.02−289.2 μM), a low detection limit (0.0026 μM), and good anti-interfering ability, acclaim its superior viability for real-time detection of TP with exceptional tolerance to the presence of foreign moieties. Hence, this work manifests that the nature of intercalants is a vital aspect to consider while designing LDH-based electrochemical probes to detect priority pollutants.