The IR, FIR, and Raman (solution and solid state) spectra of 1,3,5-triazine-2,4,6trisulfenyltrichloride ((NCSCl) 3 ) were investigated for the ®rst time. It was possible to identify all fundamentals in the solid state spectra which were assigned on the basis of a planar molecular structure with C 3h symmetry. On the other hand, the solution spectra reveal unambiguously the presence of a conformer of lower symmetry (C s ) in equilibrium with the C 3h isomer. Calculations employing the density functional theory were performed (B3LYP/6±31G*). A comparative discussion of the vibrational spectra of (NCSCl) 3 (C 3h ) with respect to those of cyanuric¯uoride ((NCF) 3 ), cyanuric chloride ((NCCl) 3 ), and cyanuric bromide ((NCBr) 3 ) reveal a signi®cant dependence of the vibrational situation within the 6-membered heterocyclic ring system on the different substituents in 2,4,6-position. Some modes of 2,4,6-trihalogeno-1,3,5-triazines have been reassigned, e.g. the normal mode v 12 of 2,4,6-tri¯uoro-1,3,5-triazine.