Dual-functional porous copper films were prepared by dynamic hydrogen bubble template (DHBT) technique to achieve in situ SERS monitoring of electrocatalytic reaction. The morphology and SERS activity of porous copper films were effectively modulated by electrolyte additive, current density, and deposition time. The interfacial evolution behaviors of porous copper films were monitored by in situ synchrotron radiation X-ray imaging. The three-dimensional porous copper films in the presence of CTAB additive present a thinner leaf-like dendritic structure and excellent SERS activity. Although the diverse morphologies of porous copper films are obtained with inorganic additives including (NH4) 2SO(4), Na2SO4, or NaCl, they are deleterious to the SERS activity due to the microstructural changes of copper films, even significantly lower than that of the additive-free condition. The obtained porous copper films exhibit high sensitivity (10(-9) mol/L) and good reproducibility for efficient SERS detection. Furthermore, the electrocatalytic reduction process of 4-nitrophenol on the porous copper films was successfully in situ monitored based on their excellent SERS activity.