In this novel, the iron(III)-PVC membrane sensor was investigated based on a new 1,1'-(iminobis(methan-1-yl-1-ylidene))dinaphthalen-2-ol (IBMYD) synthetic ionophore as a suitable carrier. The best performance was observed for the membrane composition including 33.0% PVC, 65.0% TEHP, 1.0% NaTPB and 1.0% ionophore. The electrode displayed a linear potential response over a wide concentration range from 1.0 x 10(-7) to 1.0 x 10(-1)mol L(-1), with a detection limit of 5.0 x 10(-8)mol L(-1) and a good Nernstian slope of 19.9+/-0.3 mV decade(-1). The sensor possessed some advantages such as short conditioning time, very fast response time (<12s) and especially good discriminating ability towards Fe(III) ions over a wide variety of alkali, alkaline earth, transition, and heavy metal ions. The potential response of the proposed sensor was independent of the pH of the test solution, in the pH working range from 3.0 to 6.3. The fabricated electrode was applied for at least 2 months, without any measurable divergence in the potential characteristics. The optimized sensor was used successfully for direct and indirect determination of free iron species in some different synthetic and real samples with satisfactory results.