Acetylene cyclization on S/Pd(111)has been studied using laser-induced thermal desorption with Fourier transform mass spectrometry (LITD/FTMS). The formation of benzene, thiophene, and 1,3-butadiene has been observed on the surface at low temperatures. Investigations reveal that benzene and thiophene are formed in similar amounts and that the formation kinetics of each are comparable to one another. Results also show the kinetics of benzene formation on S/Pd(111) do not differ from that on a clean Pd(111) surface, indicating that the addition of S does not significantly alter the nature of the cylization process.