Three recently synthesized Schiff’s bases were studied to characterize their ability as Cr³⁺ ion carrier in PVC-membrane electrodes. The polymeric membrane (PME) and coated glassy carbon (CGCE) electrodes based on 2-hydroxybenzaldehyde-O,O′-(1,2-dioxetane-1,2-diyl) oxime (L1) exhibited Nernstian responses for Cr³⁺ ion over wide concentration ranges (1.5×10⁻⁶–8.0×10⁻³ M for PME and 4.0×10⁻⁷–3.0×10⁻³ M for CGCE) and very low limits of detection (1.0×10⁻⁶ M for PME and 2.0×10⁻⁷ M for CGCE). The proposed potentiometric sensors manifest advantages of relatively fast response and, most importantly, good selectivities relative to a wide variety of other cations. The selectivity behavior of the proposed Cr³⁺ ion-selective electrodes revealed a considerable improvement compared to the best previously PVC-membrane electrodes for chromium(III) ion. The potentiometric responses of the electrodes are independent of pH of the test solution in the pH range 3.0–6.0. The electrodes were successfully applied to determine chromium(III) in water samples.