We investigate the optical properties and surface-enhanced Raman scattering (SERS) characteristics of metal-coated silica aerogels. Silica aerogels were fabricated by easily scalable sol-gel and supercritical drying processes. Metallic nanogaps were formed on the top surface of the nanoporous silica network by controlling the thickness of the metal layer. The optimized metallic nanogap structure enabled strong confinement of light inside the gaps, which is a suitable property for SERS effect. We experimentally evaluated the SERS enhancement factor with the use of benzenethiol as a probe molecule. The enhancement factor reached 7.9 × 107 when molecules were adsorbed on the surface of the 30 nm silver-coated aerogel. We also theoretically investigated the electric field distribution dependence on the structural geometry and substrate indices. On the basis of FDTD simulations, we concluded that the electric field was highly amplified in the vicinity of the target analyte owing to a combination of the aerogel's ultralow refractive index and the high-density metallic nanogaps. The aerogel substrate with metallic nanogaps shows great potential for use as an inexpensive, highly sensitive SERS platform to detect environmental and biological target molecules.