Abstract The a.c. polarographic determination of lanthanum(III), nickel(II), calcium (II), and magnesium(II) with diethylenetriaminepentaacetic acid was studied by using a dropping mercury electrode and a hanging mercury drop electrode as indicator electrodes. Lanthanum(III) and nickel(II) in an acetate buffer solution and calcium(II) and magnesium(II) in an ammonia buffer solution could be titrated with diethylenetriaminepentaacetic acid in the concentration range from 5×10−5 to 1×10−3 m by measuring the height of the a.c. polarographic wave of diethylenetriaminepentaacetic acid after the end point. The effect of the presence of calcium-(II) ions on the a.c. polarographic determination of lanthanum(III) in an acetate buffer solution of pH 4.0 was also examined and discussed thermodynamically.