The sufficient amounts of bis(salicylaldehyde) thiocarbohydrazone (STCH) as a lipophilic selective element (3%, w/w), sodium nitrobenzene (NB) as a plasticizer (64%, w/w), tetraphenyl borate (NaTPB) as an anionic additive (3%, w/w), and poly vinyl chloride (PVC) as a polymeric matrix (30%, w/w) was employed to form a PVC membrane of a new Pr3+ ions selective sensor to apply as an indicator electrode in analytical applications. The best electrode response was observed in the slope (19.5 ± 0.7 mV per decade) over a wide concentrations from lower (1.0 × 10−6 mol L–1) to higher (1.0 × 10−2 mol L–1) of Pr3+ ion solution with a detection limit of 8.5 × 10–7 mol L–1. This electrode showed the fast response time about 10 second for praseodymium ion concentration range of 1.0 × 10–6 to 1.0 × 10–2 mol L–1, in the pH range of 2.3–7.9. The matched potential method was applied to study the selectivity of electrode toward Pr3+ ions in comparison with many common cations. The results showed the negligible disturbance of all other cations on the proposed praseodymium(III) electrode. The making sensor has been employed successfully as an indicator electrode in the potentiometric titration of praseodymium(III) solution with EDTA at pH 6.0. Moreover the applicability of the sensor was studied in determination of Pr3+ ion in mixtures of different ions.