Different acid compositions (HNO₃, H₂O₂, HF and HClO₄) and low pressure microwave digestion were applied to the microwave assisted dissolution of ancient peats. The digests were evaluated with respect to the decomposition of the inorganic and organic fraction of peats and to an optimised determination of Pb by differential pulse anodic stripping voltammetry (DPASV). Addition of hydrofluoric acid was necessary to achieve a complete dissolution of the resistant inorganic phase of the peat and to obtain the total Pb concentration. Addition of perchloric acid decreased the concentration of dissolved organic carbon significantly, enabling reliable voltammetric signals for Pb determinations with satisfying peak shape, baseline, sensitivity, and precision. The limit of detection for Pb in peats was 1 ng/mL in the acid digest, equivalent to 0.2 μg/g in solid peat. This allowed the determination of low, pre-industrial concentrations of Pb in peat bogs from various locations (Europe and SE Asia). A chelation column used to isolate the metals from the complex matrix to further improve the detection limits failed to provide good recoveries for the peats and plants.