Copper(Cu) and nickel(Ni) complexes of para-tolualdehydesemicarbazone (pTSC) were used as carrier for an thiocyanate ion–selective electrode. The Ni(II)pTSC demonstrated higher selectivity for thiocyanate ions with better performance than Cu(II)pTSC as carrier. The electrode shows a Nernstian slope of 58.8 ± 0.3 mV decade−1 with improved linear range of 1 × 10−2 to 1 × 10−7 M and a low detection limit of 1.25 × 10−7 M in the pH range of 3–10, giving a relatively fast response and reversibility within 10 s. The selectivity coefficient was calculated using matched potential method. The electrode worked well for nearly 3 months. The response mechanism is discussed by UV-visible spectroscopic technique. The electrodes were used in potentiometric titration of thiocyanate with silver nitrate. Further, the electrode was successfully applied to determine the thiocyanate content in physiological fluids.