In a supporting electrolyte containing 6 × 10−5 M Alizarin red S, 0.2 M NH3-NH4Cl, at pH 8.2-8.6, three adsorptive complex waves of germanium-Alizarin red S have been obtained by single-sweep polarograph. The most sensitive one among them is at Ep=−1.130 V (SCE). The compositions of the complexes and the mechanism of electrode processes were studied in detail.