The effective desorption kinetic parameters of CO on the Pd(111) surface have been studied by thermal desorption spectroscopy. The zero coverage effective desorption activation energy and the preexponential factor were found to be 35.5 kcal/mol and 1013.5 s−1, respectively. As a function of CO coverage, a four-stage correlation between Ed(θ) and the development of stable low-energy electron desorption (LEED) structures was observed for the first time at Tads= 200 K. Ed and ν1 showed a strong compensation effect with Tc=519 K. The adsorption temperature dependence of Ed from Tads=87 to 200 K was observed and interpreted qualitatively by a model involving the production of different domain structures at various adsorption temperatures and the preservation of domain structures at higher coverages during temperature programmed desorption.