A poly (vinyl chloride)-based membrane of 2,3,4-pyridine-1,3,5,7,12-pentaazacyclopentadeca-3-ene with sodium tetraphenylborate(NaTPB) as an anion excluder and dioctyl phthalate (DOP) as plasticizer was prepared and investigated as a Ba(II)-selective electrode. The best performance was observed with the membrane having the ligand–PVC–DOP–NaTPB composition 1:4:1:1, which worked well over a wide concentration range (1.41×10 −6 –1.0×10 −1 molL −1 ) with a Nernstian slope of 30.0mV per decade of activity between pH 2.5 and 7.0. This electrode showed a fast response time of 18s and was used over a period of 3 months with good reproducibility (S=0.4mV). The selectivity coefficient for mono-, di- and trivalent cations indicates excellent selectivity for Ba(II) ions over a large number of cations. Electrode works satisfactorily in methanolic and ethanolic content up to a maximum of 30%. The sensor has been used as an indicator electrode in potentiometric titration of Ba(II) with EDTA.