We could prepare a novel composite consisting of a liquid crystalline polyester matrix and gold nanoparticles (7-14 nm). The polymer bears methoxy-terminated, hydrophilic, low molecular weight (350) PEG pendants on the rigid, hydrophobic aromatic polyester backbone. The polymers from a layered, sematic-like morphology at room temperature, where the interlayer is occupied by the PEG pendants. An aqueous solution of HAuCl4 was allowed to diffuse into the hydrophilic domains and the gold ions were reduced by hydrazine to gold nanoparticles. Our findings combine the concepts of self-assembly and nanoparticles, which can lead to formation of many interesting new nanocomposites.