<p>Chromium(VI), considered one of the most hazardous elements, directly affects human health and the environment. Therefore, in this study, a new approach is devised for liquid‒liquid extraction and spectrophotometric measurement of hexavalent chromium by employing a novel spectrophotometric reagent, where by 2-chlorobenzaldehyde Thiocarbohydrazone in dichloroethane is employed as a complexing reagent for chromium(VI) in the presence of potassium iodide, resulting in a yellow complex at room temperature. This approach offers a considerable benefit, being a straightforward procedure that does not require any extra solvent purification or preconcentration. The ternary [Cr(VI)–2CBTCH–iodide] complex was quantitatively recovered in dichloroethane from 3.5 mol/L hydrochloric acid medium. The maximum absorbance at λ_max = 415 nm was reached, and the sample was stable for 72 h. The method showed excellent analytical response, with a limit of detection of 0.32 μg/mL, a wide working range of up to 10.25 μg/mL, and reasonable accuracy (RSD &lt; 2%, <i>n</i> = 5). The molar absorptivity and Sandell sensitivity of the ternary complex are 0.3535 × 10⁴ L/mol∙cm and 0.0147 μg/cm, respectively, whereas 2.496 is the enrichment factor. Using the log‒log plot method, the [Cr(VI)–2CBTCH–iodide] complex composition was verified to be 1:2:2. There are no noticeable consequences of possibly interacting ions. Chromium(VI) was successfully extracted and determined simultaneously from alloy samples, contaminated water, and synthetic mixtures via this technology. The applied method has numerous advantages, including simplicity, low cost, ease of operation, rapid detection, low ligand consumption, and high sensitivity. The sensitivity of the analytical method was proven by selecting appropriate experimental conditions.</p>