Gold nanoparticles prepared by chemical reduction in sodium dodecyl sulfate (SDS) solution are size-controlled with the addition of pyrene. Micellar electrokinetic capillary chromatography (MEKC) is applied to the system to examine the size and polydispersity of gold nanoparticles and to show that pyrene has the extraordinary effect in decreasing the size and narrowing the dispersity of gold nanoparticles. The MEKC electropherograms further suggest that pyrene could be oxidized by the aqueous Au(III) complexes first. All the reduced Au complexes were then solubilized in the pyrene-SDS micelles. The growth of gold nanoparticles beyond the embryonic stage was subsequently inhibited by the encapsulating SDS and electrophilic pyrene.