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Uniform, well‐defined star‐shaped PbS nanocrystals with tunable sizes (40–100 nm, see Figure), as well as octahedral PbS nanocrystals, have been readily synthesized in aqueous solutions containing a mixture of the surfactants cetyltrimethylammonium bromide/ sodium dodecyl sulfate (CTAB/SDS) at low temperature (80 °C). The size of the PbS nanostars can be accurately controlled by adjusting the reaction time. This result may open new avenues for the green chemical synthesis of shape‐controlled semiconductor nanocrystals.