Different hexoprenaline (Hx2SO4) conventional and coated wire electrodes were constructed and evaluated. Membranes were based on hexoprenalinium phosphotungstate (Hx-PTA) and hexporenalinium phosphomolybdate (Hx-PMA). The electrodes were fully characterized in terms of their composition, response time, life span, pH, and temperature and then were applied to the potentiometric determination of the hexoprenalinium ion in its pure state, pharmaceutical preparations, and biological samples, urine and plasma, under batch and flow injection conditions. The selectivity of the electrodes towards many inorganic cations, sugars, amino acids, and some other brochodilatures of close chemical composition was also tested.