Oligomeric particles with thiol groups perpendicular to their surface were successfully fabricated in toluene. Uniform oligomer-gold nanocomposites were formed via coupling with gold nanoparticles through anisotropic Au-S interactions. Monodispersed nanoparticles consisting of one Au nanoparticle and one oligomer particle were created after dissociation in THF. Because of the simplicity of the synthetic process, our method should allow for the production of large quantities of these asymmetric nanocolloids.