Dendritic Ag/Au bimetallic nanostructures have been synthesized via a galvanic replacement reaction (GRR) of Ag dendrites in it chlorauric acid (HAuCl4) solution. After short periods of time, one obtains structures with protruding flakes; these will mature into very porous structures with little Ag left over. The morphological, compositional, and crystal structural changes involved with reaction time t were analyzed by using scanning and transmission electron microscopy (SEM and TEM, respectively), energy-dispersive X-ray spectrometry (EDX), and X-ray diffraction. High-resolution TEM combined with EDX and selected area electron diffraction confirmed the replacement of Ag with Au. A proposed fort-nation mechanism of the original Ag dendrites developing pores while growing Au flakes cover this underlying structure at longer reaction times is confirmed by exploiting surface-enhanced Raman scattering (SERS). Catalytic reduction of 4-nitrophenol (4-NP) by sodium borohydride (NaBH4) is strongly enhanced, implying promising applications in catalysis.