Gold nanoparticles (Au NPs) are nanoscale sources of light and electrons,which are highly relevant for their extensive applications in the field of photocatalysis.Although a number of research works have been carried out on chemical reactions accelerated by the energetic hot electrons/holes,the possibility of reaction pathway change on the plasmonic Au surfaces has not been reported so far.In this proof-of-concept study,we find that Au NPs change the reaction pathway in photooxidation of alkyne under visible light irradiation.This reaction produces benzil (-CO-CO-) without the presence ofAu NPs.In contrast,as indicated by surface-enhanced Raman spectroscopic (SERS) results,the C-C triple bonds (-C≡ C-)adsorbed on Au NPs are converted into carboxyl (-COOH) and acyl chloride (-COCI) groups.The plasmonic Au NPs not only provide energetic charge carriers but also activate the reactant molecules as conventional heterogeneous catalysts.This study discloses the second role of plasmonic NPs in photocatalysis and bridges the gap between plasmon-driven and conventional heterogeneous catalysis.