Gold-dendron nanocomposites have been prepared by using poly(oxymethylphenylene) dendrons (PPD) of generations (G) 1 -4 functionalized with a thiol group at the focal point as capping ligands. The mean, particle size was 1.5 and 1.4 nm for G1 and G2, respectively, with 12 and 18% of relative standard deviation, and the particle size increased for higher generations with a remarkable broadening of the size distribution. For G1 and G2, spontaneous formation of one-dimensional arrays has been reproducibly observed on carbon film, with 2.5 and 2.3 nm of line spacing for G1 and G2, respectively.