The localized surface plasmon resonances (LSPRs) of silver nanoparticles (AgNPs) give riseto the generation of so called hot electrons and a high local electric field enhancement, which enable anapplication of AgNPs in different fields ranging from catalysis to sensing. Hot electrons generated uponthe decay of LSPRs are transferred to molecules adsorbed on the surface of the NPs and trigger chemi-cal reactions via dissociative electron attachment (DEA). Herein, we report on the hot electron induceddecomposition of the brominated nucleobases – 8-bromoadenine, 8-bromoguanine, 5-bromocytosine and5-bromouracil on laser illuminated AgNP surfaces. Surface enhanced Raman scattering (SERS) spectra ofall canonical nucleobases and their brominated analogues have been recorded at different laser illuminationtimes, and for the very first time we present SERS measurements of 8-bromoguanine and 5-bromocytosine.Reaction products have been identified by their vibrational fingerprint revealing the cleavage of the carbonbromide bond in all cases even under mild illumination conditions. These results indicate that the well-known reactions from DEA experiments in the gas phase (i) are also taking place on nanoparticle surfacesunder ambient conditions, (ii) can be monitored by SERS, and (iii) are also of importance in analyticalSERS applications involving electrophilic molecules, as the bands originating from reaction products needto be identified.