Nanostructured multiphase p-type lead chalcogenides have shown the highest efficiencies amongst thermoelectric materials. However, their electronic transport properties have been described assuming homogenous distribution of dopants between phases. Here, we have analyzed elemental distributions in precipitates and matrices of nanostructured multiphase quaternary Pb chalcogenides doped to levels below and above the solubility limit of the matrix, using three-dimensional atom probe tomography. We demonstrate that partitioning of sodium and selenium occur between the matrix and secondary phase in both lightly- and heavily-doped compounds and that the concentrations of sodium and selenium in precipitates are higher than those in the matrices. This can contribute to the transport properties of such multiphase compounds The sodium concentration reached ~3 at% in sulfur-rich (PbS) precipitates and no nano precipitates of Na-rich phases were observed within either phase, a result that is supported by high resolution TEM analysis, indicating that the solubility limit of sodium in PbS is much higher than previously thought. However, non-equilibrium segregation of sodium is identified at the precipitates/matrix interfaces. These findings can lead to further advances in designing and characterizing multiphase thermoelectric materials.