Organic−inorganic hybrids have been fabricated through mild Diels−Alder cross-linking between maleimide bearing oligo(p-phenylenevinylene) (OPV) and furan functionalized gold nanoparticles with diameter smaller than 2 nm. The OPV ligands afford strong reaction ability toward furan group due to their maleimide moieties. These small gold nanoparticles form close-packed homogeneous hybrids with well-defined