We reveal nanoscale morphological changes on the surface of a silver nanowire (AgNW) in the conventional surface-enhanced Raman scattering (SERS) measurement condition. The surface morphology changes are due to the surface plasmon-mediated photochemical etching of silver in the presence of certain Raman probes, resulting in a dramatic increase of Raman scattering intensity. This observation indicates that the measured SERS enhancement does not always originate from the as-designed/fabricated structures themselves, but sometimes with contribution from the morphological changes by plasmon-mediated photochemical reactions. Our work provides a guideline for more reliable SERS measurements and demonstrates a novel method for simple and site-specific engineering of SERS substrate and AgNW probes for designing and fabricating new SERS systems, stable and efficient TERS mapping, and single-cell SERS endoscopy.