The assembly and characteristics of a copper(II) electrochemical sensor (CuES) based on β-cyclodextrin (βCD) dopped into PVC was reported in this paper. The CuES was prepared by combining Ag/AgCl reference electrode plus the polyvinyl chloride (PVC) membrane electrochemical sensor. The CuES reveals a Nernstian behavior over a wide copper ion concentration range (1.0 × 10–2 to 5.0 × 10–6 mol L–1) and a relatively low detection limit (0.32 ppm). The potentiometric response was independent of the pH of the solution above 3.9 whatever the used concentration. The CuES showed a very short response time (5 s for 10–3 and 10–2M) and (15 s for 10–4 M)) for all compositions. It exhibited very good selectivity relative to a wide variety of metal cations. The proposed CuES was used for the analysis of copper in Haematon-containing samples. This method was compared with traditional spectrophotometric techniques.