Electrochemical liquid-membrane micro-extraction is a new sample preparation strategy, which combines liquid-membrane extraction with electrochemical detection. The introduction of electrochemistry can be used to control the redox states of analytes and thereby manipulate the extraction process. The bromide in aqueous solution was electrochemically oxidized to bromine and extracted into a liquid membrane composed of ethyl benzoate supported on a graphite-epoxy composite electrode with induction of iodide redox reactions. The technique enables concentrations as low as 1 nM of bromide to be determined by cyclic voltammetry by measuring the reduction current of extracted bromine. The reduction peak current is proportional to the logarithm of bromide concentration in the range from 1 nM to 10 μM under the optimal conditions. The extraction method offers a powerful way for the electrochemical detection of trace bromide.