AbstractCalculations are reported of the total energies and related quantities of sequences of small clusters of the form AmPbn, where A is an alkali atom,n<6 andm<9. The object of this study is to shed light on the stoichiometry and the possible formation of complexes in A‐Pb liquid alloys. The calculations are performed using empty core pseudopotentials and the spherical average approximation for the cluster. The results are insensitive to the choice of alkali atom apart from a smooth trend with the progression from Li to Cs. The calculated total energies suggest that clusters with compositions A4Pb and A4Pb4are very stable against a change in the number of Pb or A atoms and support the possibility of these clusters forming in the liquid alloys. This stability arises from an electronic shell‐closing eff