Carbon paste electrodes for pancuronium bromide was prepared based on ion association complexes of pancuronium bromide with sodium tetraphenylborate (NaTPB) or ammonium reineckate using dibutyl phthalate as solvent mediator and tetradodecylammonium tetrakis-(4-chlorophenyl)borate (ETH 500) as lipophilic additive. The sensors showed a near-Nernstian slope of 28.1 mV concentration decade−1 at 25 °C within the concentration range 6.31×10−6—1.00×10−2 M in case of pancuronium-tetraphenylborate electrode and 26.6 mV concentration decade−1 in the concentration range 5.66×10−5—1.00×10−2 M in case of pancuronium-reineckate electrode. The sensors were successfully applied for the potentiometric determination of pancuronium bromide in pharmaceutical preparation and biological fluids in batch and flow injection conditions.