Monitoring trace amounts of peroxide-based molecules is challenging because of the lack of common optical signatures (fluorescence or absorption in UV-vis range) or chemical functionality easily detectable with common routines. To overcome this issue, we suggest a photochemical decomposition approach followed by the analysis of chemical fragments by a fast, sensitive, and reliable Raman spectroscopic method. To facilitate this approach, we employed a novel design of surface-enhanced Raman scattering (SERS)-active nanoporous substrate based on porous alumina membranes decorated with mixed nanoclusters composed of gold nanorods and nanoparticles. The detectable amount of HMTD below 2 pg demonstrated here is about 3 orders of magnitude lower than the current limit of detection. We suggest that laser-induced photocatalytic decomposition onto nanoparticle clusters is critical for achieving label-free detection of unstable and nonresonant organic molecules.