A variety of fluoroalkyl end-capped oligomers, such as fluoroalkyl end-capped acrylic acid oligomer [RF-(ACA) n -RF], acryloylmorpholine oligomer [RF-(ACMO) n -RF], 2-acrylamido-2-methylpropanesulfonic acid oligomer [RF-(AMPS) n -RF], 2-(methacryloyloxy)ethanesulfonic acid oligomer [RF-(MES) n -RF], and N,N-dimethylacrylamide oligomer [RF-(DMAA) n -RF], were applied to the autoreduction of gold ions to give the corresponding oligomers/gold nanocomposites, of whose sharp plasmon absorption bands are observed around 535 nm. In these fluorinated oligomers, RF-(ACA) n -RF oligomer and RF-(ACMO) n -RF were effective for the one-pot preparation of the gold nanoparticles under very mild conditions; although the other fluorinated oligomers and the corresponding non-fluorinated–(ACMO) n -oligomer were unable to afford the gold nanoparticles. RF-(ACA) n -RF/SiO2 nanocomposites and RF-(ACMO) n -RF/SiO2 nanocomposites, which were prepared by the sol–gel reactions of tetraethoxysilane in the presence of silica nanoparticles and the corresponding oligomers under alkaline conditions, were also applied to the encapsulation of gold nanoparticles into these fluorinated nanocomposite cores through the autoreduction of gold ions at room temperature. Interestingly, these fluorinated oligomers/silica nanocomposite-encapsulated gold nanocomposites before and after calcination at 800 °C were found to exhibit the same plasmon absorption band around 525 nm. RF-(MES) n -RF oligomer and RF-(AMPS) n -RF oligomer are not suitable for the autoreduction of gold ions; however, RF-(MES)n-RF[or RF-(AMPS) n -RF]/polyaniline [PAn] nanocomposites, which were prepared by the polymerization of aniline initiated by ammonium persulfate in the presence of the corresponding oligomer, enabled the formation of gold nanoparticles through the oxidation of PAn in the composites at room temperature. The reversible conformational change of PAn in the nanocomposites from the polyemeraldine salt to the oxidized pernigraniline base was observed during such oxidation process.