We successfully synthesized a series of gold nanoparticles capped with 11-(4-(pyren-1-yl)phenoxy)undecane-1-thiol (A-SH) and with 1-dodecanethiol. The homodispersed gold nanoparticles were fully verified by TEM, UV-Vis and PL spectroscopy. TEM images of the nanoparticles showed similar particle sizes at approximately 2.5 nm also evidenced by the absorption spectra. By solvent-exchange co-self-assembly of a pyrene derivative composited with these functionalized nanoparticles, the different arrangements of Au nanoparticles were observed. Compared to Au nanoparticles functionalized by 1-dodecanethiol (GNP), the pyrene–thiol-capped gold nanoparticles (GNP-A) showed better dispersity in the pyrene derivative matrix because of their π–π interactions.