Plastic membrane, coated wire and chemically modified carbon paste sensors sensitive for clomipramine hydrochloride were constructed. The sensors are based on ion-exchangers formed from association of the drug cation with anions of tetraphenylborate and silicotungestate. They were constructed and fully characterized in terms of composition, life span, response time, usable pH range, working concentration range and temperature. Improvement of these sensors behavior was carried out by using different additives. Each sensor was applied to the potentiometric determination of the drug cation in its pure solutions, pharmaceutical formulations, spiked human serum and urine samples.The drug concentration was determined in their pure solutions and tablet formulations by conductimetric titration. The solubilities, solubility products, entropy, enthalpy and free energy change of the formed ion-exchangers were also carried out applying conductimetric measurements.