Surface plasmon resonance (SPR) has been utilized in many fields, such as surface-enhanced Raman spectroscopy (SERS) and solar energy conversion. Here we developed an Au@CdS core-shell nanostructure, a bifunctional nanoparticle, used as an efficient catalyst for SPR enhanced photocatalytic degradation, and as a substrate for in situ SERS detection of methylene blue (MB) and p-nitrophenol (pNTP). With integration of an Au nanoparticle into a CdS shell, the degradation process was significantly accelerated under 500 nm long-pass (λ > 500 nm) visible light irradiation, which was caused by the injection of hot electrons. Moreover, a highly uniform, monolayer film of Au@CdS nanoparticles (NPs) has been prepared and used as both a SERS substrate and catalyst. The decomposition of MB molecules and nitrogen coupling reaction of pNTP were observed during the 638 nm laser illumination. We demonstrate that a plasmonic core-semiconductor shell nanocomposite can be a promising material for photocatalysis and in situ SERS study.