Thin layer chromatography (TLC) and gas chromatography/mass spectrometry (GC/MS) were determined to be acceptable methods for analyzing salvinorin A, the principal chemical compound of Salvia divinorum. The neoclerodane diterpene salvinorin A is an extremely potent and highly selective kappa-opioid receptor agonist. With TLC, salvinorin A was detected in raw dried leaves of Salvia divinorum and commercial Salvia divinorum extracts. It was clearly differentiated from 13 other Salvia species, Cannabis sativa L (marijuana), and salvinorins B, C, D, E, and G. The latter occur in the Salvia divinorum plants at lower concentrations than salvinorin A. When using GC/MS, salvinorin A was best extracted from plant material with chloroform at an ambient temperature when using a nonpolar solvent and acetone at an ambient temperature when using a polar solvent. By using these two techniques, criminalists are now able to confirm the presence of salvinorin A in a submitted plant material suspected to be Salvia divinorum. The studies used raw dried leaves of Salvia divinorum and commercial Salvia divinorum extracts purchased in June 2007 from the HerbalFire Web site. HerbalFire guarantees 25 mg of salvinorin A per gram of leaf in the “10x” and 12.5 mg of salvinorin A per gram of leaf in the “5x.” The Cannabis sativa L (marijuana) and the 13 species of Salvia were provided by the controlled substances unit of the San Bernardino County Sheriff’s Department’s Scientific Investigations Division. In addition to descriptions of the plant material and Salvinorin standards, the descriptions of materials and methods cover TLC and GC/MS procedures, as well as extraction techniques used by surveyed crime laboratories. 2 tables, 7 figures, and 6 references