Na2Ti3O7 (NTO) is recognized as an authenticated promising photocatalyst and surface-enhanced Raman scattering (SERS) active material, although its performance is limited by its high carrier recombination rate, wide band gap and inadequate utilization of visible light. In this study, to solve these issues, sea urchin-shaped NTO nanowires directly grown on a substrate were fabricated, and then Ag nanoparticles were decorated on NTO nanowires using sputtering equipment. The as-prepared Ag-NTO substrates exhibited different morphologies and high SERS activity, which was confirmed by finite-difference time-domain (FDTD) simulations, showing that appropriate Ag decoration can bring more nanogaps and thus enhance the electromagnetic field (EM) contribution. We visualized the charge transfer (CT) mechanism in SERS and further investigated the catalytic hydrogen production process similarly induced by photogenerated CT. The optimal SERS substrate (Ag-NTO-3) was adopted to verify the photocatalytic hydrogen evolution (PHE) activity, and the hydrogen evolution rate of Ag-NTO-3 was 106.7 μmol h-1 (twice that of pristine NTO). Photoelectrochemical measurements and photoluminescence (PL) analysis were used to elucidate the potential enhancement mechanisms for the photocatalytic performance and CT process. This study can provide a valuable reference for performance and mechanism studies of SERS substrates and photocatalysts.