We reassess literature data and demonstrate that the intermolecular hydrogen transfer occur likely during the primary catalytic interaction between thiophene molecules, rendering it the credible thiophene hydrodesulfurization (HDS) pathway. Deuterium tracer experiments prove that thiophenic hydrogen plays a part in direct C-S cleavage, in the initial step of thiophene HDS. Hypothetical surface intermediates for thiophene exchange do not precede, i.e. do not form prior to the surface intermediates for thiophene HDS. Therefore the established thiophene exchange/HDS scheme and the sequence of events are not the viable concepts. Since the deuterium data also indicate that C4H5S(a)-radicals are not formed this means there are no common surface or reaction intermediates for the thiophene exchange and HDS and both reactions proceed parallel.