Here, using the (Au/TiO2)-catalyzed reduction of 4-nitrothiophenol as a probe reaction, a catalysis/SERS bifunctional composite fabricated by uniformly dispersing catalysis-active Au nanoclusters (∼2 nm) on a SERS-active TiO2 photonic microarray was successfully applied to the non-plasmonic SERS self-monitoring of a catalytic reaction for the first time, which is superiorly sensitive and interference-free.