A new approach to the determination of the parameters of polarographic catalymetry using ligand catalysis have been developed. The following parameters were determined for the model electrocatalytic systems Ni2+ + pyridine and Ni2+ + pyridine + acetate : (1) quantitative characteristic for the existence of the catalytic prewave : (2) the value of the catalytic effect; (3) the detection limit of the ligand catalyst; (4) quantitative characteristic for the existence of the optimum analytical signal.