Molecular beam scattering techniques are used to explore the energy exchange and thermal accommodation efficiencies of HCl in collisions with long-chain OH- and CH3-terminated self-assembled monolayers (SAMs) on gold. Upon colliding with the nonpolar methyl-terminated SAM, HCl (E-i = 85 kJ/mol) is found to transfer the majority, 83%, of its translational energy to the surface. The extensive energy loss for HCl helps to bring the molecules into thermal equilibrium with the monolayer. Specifically, 72% of the HCl approaches thermal equilibrium prior to desorption. For the molecules that do not thermally accommodate, but scatter after an impulsive collision with the surface, the final translational energy is observed to be directly proportional to the surface temperature as the thermal surface energy and gas translational energy exchange during the collision. For the OH-terminated SAM, the impulsively scattered HCl escapes from the surface with slightly more average energy. The rigid nature of the OH-terminated SAM is due to the extended intra-monolayer hydrogen-bonding network that restricts some of the low-energy modes of the surface. However, despite the rigid nature of this system, the extent of thermal accommodation for HCl on these two surfaces is remarkably similar. It appears that the potential energy well between the impinging HCl and the polar surface groups is sufficient enough to trap HCl molecules that would otherwise scatter impulsively from this rigid SAM.