We describe a composite material for use in electrochemical oxygen reduction. A screen-printed electrode (SPE) was consecutively modified with electrodeposited copper, a Nafion membrane and electropolymerized polyaniline (PANi) to give an electrocatalytic composite of type PANi/Nafion/Cu2O/SPE that displays good electrical conductivity at neutral pH values. It is found that the presence of ammonia causes complex formation with Cu(I), and this causes electroreduction of oxygen to result in an increased cathodic current. The finding was applied to the quantification of ammonium ions in the 1 to 1000 μM concentration range by amperometry at −0.45 V (vs. Ag/AgCl). This Faradaic phenomenon offers the advantage of direct voltammetric detection, one of the lowest known limits of detection (0.5 μM), and high sensitivity (250 mA∙M−1∙cm−2). It was applied to the determination of ammonium ion in human serum where it compared well with the photometric routine approach for clinical analysis using glutamate dehydrogenase.