Plasmonic nanostructures stand at the forefront of nanophotonics research, particularly in sensing and energy conversion applications. Their unique ability to confine light energy at the nanoscale makes them indispensable for a wide array of technological advancements. The study of these structures often makes use of different materials and, even more extensively, explores new shapes and configurations to extend our common repertoire of useful nanophotonics tools. Exploring the creation of bimetallic plasmonic nanostructures combines these two dimensions determining the space of possible plasmonic resonators and opens the possibility of tailoring systems with behavior unavailable to single-metal plasmonic structures. In this paper, we delve into the exploration of bimetallic systems employing plasmonic nanostars. These structures have demonstrated remarkable capabilities for surface-enhanced Raman scattering (SERS) spectroscopy and photochemistry, due to the strong plasmonic response of their peaks, whose disposition following a spherical symmetry makes them largely polarization- and orientation-insensitive. Herein, we report the colloidal synthesis of two different water-stable Au@Ag nanostars, explore their performance as photocatalysts and SERS substrates, and provide an in-depth account of their non-trivial physical response.