Chromium is one of the most notorious environmental pollutants. The development of a sensitive and selective chromium detection method is an important issue. In this paper, cation recognition properties of two benzyl-functionalized benzimidazolylidene ligands towards metal ions were investigated by UV–vis spectrophotometry. The results showed that the receptors had a higher selection of Cr3+. The important analytical parameters, such as pH, quantity of the reagents, and their effects on the studied system were investigated. Under the optimum conditions the absorbance of the Cr3+-L complex obeys Beer's law in the Cr3+ concentration range of 0.05–2.60 μg/mL with the limit of detection of 0.026 and 0.034 μg/mL for L1 and L2, respectively. Infrared (IR) spectrum and density functional theory (DFT) calculations were used to explore the coordinating sites and the complex strength of two ligands towards Cr3+. The thermodynamic parameters showed that complex formation is a spontaneous exothermic process. The proposed method was successfully applied to the determination of Cr3+ content in water and alloy samples. The proposed method is seen as a simple and effective way of determining Cr3+ concentration.