A new method to fabricate an Au-rich interconnected ligament substrate by dealloying the Au-based metallic glass ribbon for surface-enhanced Raman scattering (SERS) applications was investigated in this study. Specifically, three substrates, Au film, Au-based metallic glass ribbon, and dealloyed Au-based metallic glass ribbon, were studied. The dealloyed surface showed ligament nanostructure with protruding micro-islands. Based on the field emission scanning electron microscopy, reflection and scattering measurements, the dealloyed Au-based metallic glass provided a large surface area, multiple reflections, and numerous fine interstices to produce hot spots for SERS enhancements. The SERS signal of analyte, p-aminothiophenol, in the micro-island region of dealloyed Au-based metallic glass was about 2 orders of magnitude larger than the flat Au film. Our work provides a new method to fabricate the inexpensive and high SERS enhancements substrates.