Gold nanoparticles capped by an unsymmetrical azobenzene disulfide, 4-hexyl-4‘-(12-(dodecyldithio)dodecyloxy)azobenzene (C6AzSSC12), were synthesized in order to investigate the efficiency of azobenzene photoisomerization on colloidal gold surfaces. The nanoparticles were synthesized by a two-step method to avoid the direct contact of azobenzene units with a reducing agent. The average size of the particles was determined to be ∼5.2 ± 1.3 nm from transmission electron microscope (TEM) images. The CH2 antisymmetric (∼2919 cm-1) and symmetric (∼2850 cm-1) stretching bands in the FTIR spectra of the nanocomposite confirmed the all-trans conformation of alkyl chains in the C6AzSSC12 on the colloidal gold. The photoisomerization reaction of the C6AzSSC12-capped gold nanoparticles was studied by UV−vis absorption spectroscopy in toluene. The reaction kinetics was identical to that of the free C6AzSSC12 molecules dissolved in toluene, with no deviations from a first-order plot for both trans-to-cis and cis-to-tr...