The novel starlike PbS particles were successfully synthesized for the first time in a mixed system of poly - (styrene-alt-maleic acid) (PSMA) and cetyltrimethylammonium bromide (CTAB). The as-prepared hierarchically starlike PbS particles have six symmetric perpendicular arms or arm groups, each of which consists of parallel rods or ellipsoids that are perpendicular to the arm. Moreover, spherical and cubic-shaped PbS particles were facilely produced via varying the concentration of CTAB in the mixed system. The presence of CTAB in the mixed system played a key role in the formation of unusual PbS stars. The faster growth rate in six (100) directions of PbS crystals induced by the organic additives were thought to be responsible for the formation of such novel starlike PbS particles. (c) 2006 Published by Elsevier B.V.