The influence of Pb2+ on the initial stages of Sn electrodeposition onto copper from methyl sulphonic acid solutions in the absence of organic additives has been investigated. Particular attention is placed on the effect of Pb2+ at concentrations much lower than previously reported and where no lead is detected in the resulting deposit. Linear sweep scans and i-t transients show that Pb2+ catalyzes Sn plating at Pb2+:Sn2+ molar concentration ratios between about 1:1000 and 20:1000. This effect can be significant, with as much as a 30% increase in the amount of tin deposited over that obtained in the absence of Pb2+ when the concentration ratio is 2:1000 or 5:1000. At concentration ratios above 20: 1000, the effect disappears and in fact, Pb2+ has an inhibitory effect on Sn2+ reduction. Under conditions where Pb2+ enhances Sn electrodeposition. it also begins to affect electrocrystallization by promoting faster nucleation and a more 2-dimensional coating that more rapidly covers the substrate. This trend continues as the Pb2+ concentration is further increased and the catalytic effect disappears. (c) 2007 Elsevier Ltd. All fights reserved.