The polarographic waves of lead (II) and tin (II) overlap due to their similar reductive potentials and it is difficult to determine these two components simultaneously without a pre-separation. In this paper, differential pulse polarography (DPP) combined with multivariate calibration approaches, such as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS), were successfully applied to the resolution of overlapping polarographic waves of these two components in the concentration range of 0.05-3.50 mg 1−1. Satisfactory quantitative results were obtained.