A novel Schiff base designated as 5-[(3-methylthiophene-2-yl-methyleneamino)]-2-mercaptobenzimidazole was synthesized and characterized. A polyvinyl chloride-membrane potentiometric copper(II)-selective sensor was prepared by using the synthesized 5-[(3-methylthiophene-2-yl-methyleneamino)]-2-mercaptobenzimidazole compound. The prepared polyvinyl chloride-membrane copper(II)-selective sensor exhibited very good selectivity and sensitive potentiometric response towards copper(II) ions compared to a wide variety of other cations. The sensor had a fast response time of <5 s, and showed a linear Nerstian behavior to copper(II) ions over a wide concentration range from 1.0 x 10(-5) to 1.0 x 10(-1) mol L-1 with a slope of 29.2 +/- 0.7 and correlation coefficient of 0.9998. The prepared polyvinyl chloride-membrane copper(II)-selective sensor was used for 14 weeks without any significant change in its potentiometric response. The potentiometric response of the developed sensor was highly repeatable. Additionally, the developed sensor was used as an indicator electrode for the potentiometric titration of copper(II) ion with ethylenediaminetetraacetic acid. The sensor was also successfully applied to the direct determination of copper(II) ions in tap water, river water, and dam water samples.