Fast-scan anodic stripping voltammetry (FSASV) was applied to sensitively detect Pb2+ on a mercury film electrode (MFE). The method was involved with a controlled preconcentration by accumulation of Pb2+ on the MFE followed by FSASV measurement. At the scan rate of 500 V/s, a linear relationship between the anodic stripping peak current and the logarithm of Pb2+ concentration in the solution was observed in the range from 0.1 µmol/L to 0.1 pmol/L with a detection limit of 0.1 pmol/L. The proposed method was successfully applied for the determination of Pb2+ in spiked water samples with satisfying recoveries in the range of 98.6 to 104.3%, and the corresponding relative standard deviation ranged from 3.7 to 5.5%. Therefore, FSASV is a sensitive, fast, cost-effective and simple method for the detection of Pb2+ at picomolar level and would be very promising in heavy metal determination.