The reactivity of the dilithioplumbole ([Li2(thf)2(μ,η5-LPb)], LPb = 1,4-bis-tert-butyl-dimethylsilyl-2,3-bis-phenyl-plumbolyl) towards the reactive pnictogen precursors P4, pentaphosphaferrocene, and pentaarsaferrocene ([Cp*Fe(η5-E5)] (Cp* = η5-C5Me5, E = P, As)) is reported. The reaction with P4 afforded a phospholyl lithium complex, via lead-phosphorus exchange, while the reactions with [Cp*Fe(η5-E5)] yielded the first examples of Pb–Fe–Li heterotrimetallic triple-decker polypnictogenides with three different deck motifs