The decomposition of 1,1-dichloroethene on Pd(111) is investigated using conventional thermal desorption, laser-induced thermal desorption (LITD), and FT reflection absorption infrared spectroscopy (FT-RAIRS). The decomposition mechanism produces at least three hydrocarbon surface intermediates, including ethylidyne. Thermal desorption results differ between high and low coverages because of relative surface concentrations of Cl and H in combination with kinetic effects.