Smoking of Salvia divinorum leaves is the most common method for its psychotropic effects. Eleven thermal degradation products, including a new neoclerodane diterpene derivative, were isolated from the smoke of S. divinorum leaves, and their structures were identified by spectroscopic methods. The isolated compounds were evaluated for their binding affinities at the opioid receptors, and salvinorin A is still the most potent kappa opioid receptor agonist.