The herbicides azafenidin [(2-(2,4-dichloro-5-prop-2-ynoxyphenyl)-5,6,7,8-tetrahydro-[1,2,4]triazolo[4,3-a]pyridin-3-one)] and flumetsulam [(N-(2,6-difluorophenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-2-sulfonamide)] were subjected to IR, Raman, UV-Vis and emission studies. As triazolopyridine is the most prominent and active component of these herbicides, this molecule was characterised by XRD studies, FTIR, Raman, UV-Vis and emission spectra. The experimental data were compared to the results of the DFT quantum chemical calculations carried out for its optimised structure, IR intensities and Raman activities, HOMO-LUMO transitions, and energies of the singlet and triplet states. The characteristics for triazolopyridine quantities were used in the analysis of the studied herbicides.