A series of Janus composite poly(3-hexyl thiophene)-b-poly(3-thiophenehexanethiol)-gold nanoparticles were synthesized by self-assembly at the water-oil interface, and their photoelectric performance was investigated. The results show that the precise Janus composite nanostructure could be controlled by the adjustment of the reaction temperature and stirring time. The UV-visible measurement revealed that the absorption maximum had an appreciable redshift, and the photoluminescence (PL) spectra indicated that the PL intensity of poly(3-hexyl thiophene)-b-poly[3-(6-thiolhexyl thiophene)] decreased upon the addition of gold nanoparticles. In addition, compared to a common composite of poly(3-hexyl thiophene), the conductivity properties of the Janus composite nanostructure increased remarkably. Therefore, the Janus composite nanoparticles have the potential for applications in photovoltaic devices.