The polarographic behavior of prilocaine as its N-nitrosamine derivative, was studied using several electrochemical techniques. In acidic media, a nonreversible diffusion controlled reduction process involving two electrons takes place (E1/2=−0.86 V at pH 3.5). A differential pulse polarographic method is described for determining prilocaine based on the formation of its N-nitrosamine derivative in aqueous solution. The method has been validated for a series of artificial matrices where different functional groups are present. It was also applied to a pharmaceutical formulation.