An amperometric procedure for the measurement of magnesium(II) has been developed using the enzyme hexokinase in solution and glucose oxidase immobilized onto a preactivated polymeric support. The reaction of hexokinase was monitored following the decrease in current due to the glucose consumption by the enzyme in the presence of the ATP-Mg2+complex. The reaction rate was dependent on the concentration of magnesium(II) in solution. Concentrations of hexokinase and ATP were optimised. Measuring the current change in the 1-3 min interval after the start of the reaction magnesium(II) can be determined in the 4 × 10−5to 10−3M range. Other divalent cations tested showed no interference. The magnesium(II) content of 5 pharmaceutical products was measured with the amperometric and compared to a spectrophotometric procedure. The results correlated well.