AbstractRelative signs of1J(207Pb13C) and2J(207Pb1H) were determined for numerous methyllead derivatives by observing the207Pb satellites in two‐dimensional (2D)13C/1H heteroscalar correlated NMR spectra. The compounds studied include the species [R3Pb]Li (R = Me, 1a, Et 1b), Me3PbSiMe3(2), [Me3PbBH3]Li, several alkenyltri‐methyllead compounds and some heterocyclics. Together with the linear correlation between1J(207Pb13CMe) and1J(119Sn13CMe) for the corresponding tin compounds, this enables the prediction of the absolute sign of1J(207Pb13CMe). An analogous linear correlation1J(207Pb13CC=)/1J(119Sn13CC=) exists which explains some apparently anomalous values reported in the literature, e.g. for [Ph3Pb]Li and for an intramolecular‐base‐stabilized plumbylene. The two coupling constants,1J(207Pb13CMe), for the Me2Pb group in a 2,5‐dihydro‐1,2,5‐azoniaplumbaboratole are of opposite sign, giving the first example of this type of behaviour for any dimethyl element fragment. In the case of 2 the negative sign of1J(207Pb29Si) [reduced coupling constant1K(207Pb29Si)>0] has been deduced from the tilt of the207Pb satellites in the 2D29Si/1H heteroscalar correlated NMR spectrum. A positive sign of1J(207Pb11B) follows from the consistent trend observed for the reduced coupling constants1K(M11B) and1K(M13C) (M =13C,29Si,119Sn,207Pb) in the series of compounds [Me3MBH3]Li and Me4M,