In this study, poly (vinyl chloride)(PVC) membrane electrodes with/without multi-walled carbon nanotubes (MWCNTs) based on a calix[4]arene derivative for perchlorate ion were described. The influence of membrane composition, pH, conditioning solution on the potentiometric response of the electrodes was investigated. Perchlorate-selective PVC membrane electrode exhibited a slope of 47.8 ± 0.6 mV/pClO4 in the range of 1.0 × 10−7–1.0 × 10−1 mol L−1at pH 4.0 while the coated Pt electrodes with MWCNT-OH, MWCNT-COOH and MWCNT displayed slopes of 46.1 ± 0.7 mV/pClO4 (5.0 × 10−6–1.0 × 10−1 mol L−1), 50.4 ± 1.9 mV/pClO4 (1.0 × 10−6–1.0 × 10−1 mol L−1) and 44.4 ± 0.3 mV/pClO4 (1.0 × 10−5–1.0 × 10−1 mol L−1), respectively. Other response characteristics of these electrodes such as response time, lifetime and detection limit were identified, and the selectivity coefficients towards various anions were calculated by separate solution method. Moreover, the perchlorate-selective electrodes described here were successfully used as an indicator electrode for the determination of perchlorate in real samples such as tap water, river water and human urine by direct calibration method.