The use of conjugated polymers (CPs) and metallic nanoparticles is an interesting way to form nanocomposites with improved optical properties. For instance, a nanocomposite with high sensitivity can be produced. However, the hydrophobicity of CPs may hamper applications due to their low bioavailability and low operability in aqueous media. This problem can be overcome by forming thin solid films from an aqueous dispersion containing small CP nanoparticles. So, in this work we developed the formation of thin films of poly(9,9-dioctylfluorene-co-3,4-ethylenedioxythiophene) (PDOF-co-PEDOT) from its natural and nano form (NCP) from aqueous solution. These copolymers were then blended in films with triangular and spherical silver nanoparticles (AgNP) for future applicability as a SERS sensor of pesticides. TEM characterization showed that the AgNP were adsorbed on the NCP surface, forming a nanostructure with an average diameter of 90 nm (value according to that obtained by DLS) and with a negative potential zeta. These nanostructures were transferred to a solid substrate, forming thin and homogeneous films with different morphology of PDOF-co-PEDOT films, as observed by atomic force microscopy (AFM). XPS data demonstrated the presence of the AgNP in the thin films, as well as evidence that films with NCP are more resistant to the photo-oxidation process. Raman spectra showed characteristic peaks of the copolymer in the films prepared with NCP. It should also be noted the enhancement effect of Raman bands observed on films containing AgNP, a strong indication of the SERS effect induced by the metallic nanoparticles. Furthermore, the different geometry of the AgNP influences the way in which the adsorption between the NCP and the metal surface occurs, with a perpendicular adsorption between the NCP chains and the surface of the triangular AgNP.