Plasmonic superstructures may concentrate hot spots both on the external surface and within the inner gaps of the assembly. However, these materials are usually obtained by two-steps procedures from synthesis of plasmonic nanoparticles to their 3D assembly. The interconnected nano-network of water and oil channels in a bicontinuous microemulsion (BμE) may act as a preorganized reaction system giving reticulated materials. In this work, a silver hierarchical superstructure (HSS-AgCt) was obtained in the water channels of a BµE in a one-pot procedure. The characterization of the morphology and crystalline structure revealed that this superstructure is composed of silver nanoparticles embedded in polymeric silver citrate forming a 3D mesh of interconnected fibers with mean width of 30 nm. The aging of HSS-AgCt in the BμE allowed the degradation of the citrate fibers giving rise to interconnected spherical silver nanoparticles (HSS-Ag) of 8 nm as measured from TEM images. Rhodamine 6-G was detected by SERS up to 10-12 M with an analytical enhancement factor of 109 for both materials using a 633 nm laser operating at 0.85 mW (5% of the nominal power). These results introduce a novel route to obtain highly sensitive SERS substrates in one-pot procedures by using BμE as a nanoreactor and template.