The present study demonstrates an original approach by which Au nanoparticles (similar to 10 nm) are embedded into TiO2 fibers via electrospinning. The photocatalytic performance of the resultant fibrous material was studied and related to the architecture and the nature of the internal interfaces in the composite. It was found that embedment of nano Au particles into the TiO2 fiber significantly improved the photocatalytic performance as compared to non-embedded ones. Electrospun fibers with the Au nanoparticles (similar to 10 nm) showed an average fiber diameter of similar to 380 nm. The photocatalytic studies of Au embedded TiO2 fibers using ultra-violet (UV) visible spectroscopy showed similar to 35% increase in photocatalytic activity when compared to the TiO2 fibers without the Au nanoparticles after 7 hrs of UV irradiation. This increase in photocatalysis was attributed to the ability of Au to increase charge separation in TiO2 and also to the ability of Au to transfer plasmonic energy to the dye.