A simple indirect method using aluminum chelating drugs as electroactive complexation ligands for the voltammetric determination of aluminum in environmental and biological samples on glassy carbon working electrode is studied. In the range of pH 8–9, desferrioxamine (DFO), 1,2-dimethy-3-hydroxypyrid-4-one (Hdmp), 3-hydroxy-2-methyl-4H-pyran-4-one (Hma) and 2,3-dihydroxypyridine (DHP) yielded good anodic peaks. It was demonstrated that the decrease of the anodic peak current of the drugs was linear with the increase of aluminum concentration. Among them, Hdmp was found the best complexible ligand and chosen for the voltammetric determination of aluminum with EDTA as chelant, which was used for masking most of the interferences. Under the optimum experimental conditions, the linear range for determination of Al by Hdmp was 5×10−7–3×10−5 mol L−1 Al(III), the detection limit was 2×10−7 mol L−1, and the relative standard deviation for 3×10−6 mol L−1 Al(III) was 2.6% (n=7). The proposed method was applied to the determination of Al in real water samples and biological samples. The Al concentration in serum samples can be measured directly without time-consuming digestion pretreatment.