A miniaturized solid-contact polyvinyl chloride membrane electrode based on the bis[(2-(hydroxyethylimino)phenolato]copper(II) complex has been prepared for the determination of Cu(II) ion in real samples. The influence of coating membrane composition, pH, and possible interfering cations on the response of the ion-selective electrode was investigated. A number of membranes at different compositions were prepared and their Cu2+ sensing capabilities were investigated. The best results for Cu2+ sensing was obtained for the electrode membrane containing ionophore − 2-nitrophenyloctyl ether – polyvinyl chloride and potassium tetrakis(p-chlorophenyl)borate in a ratio of 4:65:30:1 (w/w, mg), respectively. The prepared electrode exhibited a near-Nernstian response (28.3 mV/decade) to Cu2+ in the concentration range from 1.0 × 10−6 to 1.0 × 10−1 mol/L with a limit of detection of 8.3 × 10−7 mol/L. The potentiometric response of the electrode was independent from the pH of the test solution in the pH range of 3.0–6.0. The electrode has a very short response time, about 15 s, and it can be used over a period of 3 months without any divergence in potential. The electrode has been successfully applied as an indicator electrode in potentiometric titration of Cu(II) ions with ethylenediaminetetraacetic acid and in the determination of Cu(II) in wastewater of the copper processing industry.