The study of electrochemical behavior of aluminum–cupferron complex indicated that aluminum and cupferron formed complex in 0.4 mol/L (NH 4) 2SO 4 solution. Accumulation potential of −0.95 V (vs. SCE) was applied, while the solution was stirred for 60 s. The response curve was recorded by scanning the potential to the negative direction and the peak current of −1.18 V (vs. SCE) was recorded. This complex absorbed in hanging mercury drop electrode (HMDE) and create a sensitive peak current. The peak current and concentration of aluminum accorded with linear relationship in the range of 4.0 × 10 −8–2.0 × 10 −9 g/mL. The relative standard deviation (at 10 μg/L) is 3.0% and the detection limit is 8 × 10 −10 g/mL. The interference of some common ions was studied. This method has been used to determine trace aluminum in foods and water.