A sensitive complex absorptive wave of Ca-ARS was obtained by using differential pulse voltammetry when a mercury film glass carbon electrode was immersed in 0.1 mol L−1 KOH and 4.5×10−4 mol L−1 ARS solution. The peak potential obtained was −1.17 V (vs Ag-AgCl). The peak current was proportional to the concentration of calcium in the range of 5.0×10−8−4.2×10−5 mol L−1. The detection limit was 2.0×10−8 mol L−1. This method was applied successfully to determining traces of calcium in blood serum. The electrochemical behavior of the system was also studied by cyclic voltammetry, and the experiment results showed that the electrode process was an irreversible absorptive with two electrons participating.